TW591338B - Bases and surfactants and their use in photoresist compositions for microlithography - Google Patents

Abstract

A photoresist composition having: (A) a polymer selected from the group consisting of: (a) a fluorine-containing copolymer having a repeat unit derived from at least one ethylenically unsaturated compound characterized in that at least one ethylenically unsaturated compound is polycyclic; (b) a branched polymer containing protected acid groups, said polymer comprising one or more branch segment(s) chemically linked along a linear backbone segment; (c) fluoropolymers having at least one fluoroalcohol group having the structure: -C(Rf)(Rf')OH, wherein Rf and Rf' are the same or different fluoroalkyl groups of from 1 to about 10 carbon atoms or taken together are (CF2)n wherein n is 2 to 10; (d) amorphous vinyl homopolymers of perfluoro(2,2-dimethyl-1,3-dioxole) or CX2=CY2 where X=F or CF3 and Y=-H or amorphous vinyl copolymers of perfluoro(2,2-dimethyl-1,3-dioxole) and CX2=CY2; and (e) nitrile/fluoroalcohol-containing polymers prepared from substituted or unsubstituted vinyl ethers; (B) at least one photoactive component; and (C) a functional compound selected from the group consisting of a base and a surfactant. The polymer may have an absorption coefficient of less than about 5.0 mum<-1> at a wavelength of about 157 nm. These photoresist compositions have improved imaging properties.

Description

591338 A7 --- __________ B7 V. Description of the invention (1 ^-璧 Lming background invention scope of the invention # _ 于 光 成 相 'and especially photoresistance (positive operation and / or negative operation) in semiconductor components Manufacturing uses for imaging. The present invention also relates to new particles and surfactants, which are used together with polymer compositions having high UV transparency (especially at short wavelengths such as 157 nm and 193 nm). Use 'and it can be used in photoresist and potentially in many other applications. BACKGROUND OF THE INVENTION Polymer products are used as components of imaging and photosensitive systems, and especially in photophase systems, such as lithographic etching. Introduction to L2 Thompson, CC G. Willson, and Mj Bowden, American Chemical Society (Washington, DC), 1994. In this type of system, ultraviolet (UV) or Other electromagnetic radiation impinges on a substance containing a photoactive component to cause physical or chemical changes in the substance. A usable or potential image is then generated that can be processed into a useful image for the manufacture of semiconductor components. The combination product itself may be photoactive, but in general, the photosensitive composition contains one or more photoactive components in addition to the polymer product. The photoactive components are used to modify the photosensitivity when exposed to electromagnetic radiation (such as UV light). Rheological state, solubility, surface characteristics, refractive index, color, electromagnetic characteristics, or other such physical or chemical characteristics, as described in Thompson et al., As described in previous publications. In semiconductor devices At the sub-micron level, it is necessary to image extremely fine surface features, and electromagnetic radiation in far or extreme ultraviolet (UV) light is necessary. -5- This paper size applies to China National Standard (CNS) A4 (210 X 297) (Mm) A7 B7 V. Description of the invention (2) Positive operation photoresist is usually used in semiconductor manufacturing. In UV, under 365nm (I-line), novolac polymer and diazo group are used. The etching technique of Zhaig Kun as a dissolution inhibitor is a wafer technology that has been established at present, with an analytical limit of about 0.35-0.30 microns. In far UV, at 248 nm, the use of p-hydroxystyrene polymer Etching, which is known and has an analytical limit of 0.35-0.18 nm. There is a strong motive force for future photoetching at even shorter wavelengths. This is because the lower resolution limit is reduced as the wavelength is reduced (meaning 'yes The resolution limit for imaging at 193 nm is 0.018 μm, and the resolution limit for imaging at 157 nm is about 0.07 μm. The exposure wavelength of 193 nm (from argon fluoride (ArF) excimer thunder) is used. Photolithography is a future candidate for the microelectronics industry using 0.18 and 0.13 micron design rules. Photolithography using a 157nm exposure wavelength (derived from a fluorine excimer laser) is a further step Future candidates for lithography (above 193 nm) beyond the current level, provided that suitable substances with sufficient transparency and other required properties at this extremely short wavelength can be found. The traditional near-UV and far-UV organic photoresistors' opacity at 193 nm or shorter wavelengths prevents their use in single-layer systems at these short wavelengths. However, there is still a need for a photoresist composition that meets various requirements for a single layer of photoresist, including optical transparency at 193 nm and / or 157 nm, resistance to electrical etching, and resistance in aqueous inspection imaging agents. Solubility, and in line with the required imaging properties. In the positive-tone photoresist, there is a constant demand for improved analysis. — Previously, for this kind of chemically amplified photoresist, it has been found that the addition of a small amount of alkali can significantly improve various imaging properties, such as resolution, image distribution, -6-This paper scale applies the Chinese National Standard (CNS) A4 specification (21〇 χ 297 mm) 591338 A7 ____B7_ 1. Description of the invention (3 ~ —focus depth and processing latitude. It is generally considered that it is controlled by the diffusion of acid (produced by exposure of photoacid generator) to unexposed or Occurs in poorly exposed areas. Surfactants that have been previously added to photoresist formulations have been found to improve the coatability and / or developability of such photoresist compositions, resulting in improved imaging The invention is based on testing and / or the use of surfactants in photoresist formulations, and is found at low wavelengths, typically at or below about 193 nm, and more typically at Or less than about 157 nanometers is a combination of optically transparent substances. In a first aspect, the present invention provides a photoresist composition comprising: (A) at least one polymer selected from the group consisting of: 气 gas-containing copolymerization Comprising repeating units derived from at least one ethylenically unsaturated compound, characterized in that the at least one ethylenically unsaturated compound is polycyclic; (b) a branched polymer containing a protected acid group, the polymerizing The body contains one or more branched segments that are chemically connected along the linear main segment; (c) a fluoropolymer having at least one fluoroalcohol group having the following structure:

-C (Rf) (Rf,) 0H wherein Rf and Rf · are the same or different fluoroalkyl groups of 1 to about 10 carbon atoms, or are used together as (CF2) n, where η is 2 to about 10; ⑷Perfluoro (2 &gt; dimethyl-fluorene, 3-dioxolene) or CXfCY2 is not applicable to the Chinese paper standard (CNS) A4 (210X297 public binding)

Line 591338 A7 B7 V. Description of the invention (4 crystalline ethylenic homopolymer, where X = F or CF3, and γ = -Η, or perfluoro (2,2-dimethyl-1,3-dioxo Limonene) and amorphous ethylene-based copolymers thereof; and (e) polymers containing, for example, / fluoro alcohols, made from substituted or unsubstituted vinyl ethers; and (B) at least one photoactive component; And (C) a functional compound selected from the group consisting of a base and a surfactant. In a second aspect, the present invention provides a method for preparing a photoresist image on a substrate, including the following sequence: (X) making a photoresist layer Exposure by image copying to form imaged and unimaged areas, wherein the photoresist layer is made from a photoresist composition comprising: (A) at least one polymer selected from the above-mentioned ⑷-⑷; (B) -A photoactive component; and (C) a functional compound selected from the group consisting of a base and a surfactant; and (Y) developing an exposed photoresist layer with imaged and unimaged areas to form relief The image is on a substrate. This base may have a pKa of about 5 or greater. This base may be selected from the group consisting of at least one monomeric nitrogen compound Polymeric nitrogen compounds, organic amines, organic ammonium hydroxide, and salts with organic acids. This surfactant can have a positive, negative, or neutral charge and can be selected from fluorinated or unfluorinated surfactants 。 The best Zen Chan with bumper application -8- This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm). The binding line is 1338 A7 ___B7 5. Description of the invention (5) This photoresistive element It includes a carrier and at least one photoresist layer; wherein the photoresist layer is made from a photoresist composition, which comprises: (A) selected from a polymer including the above (a) to (e), and a mixture thereof; (B ) Photoactive ingredients; and (C) selected from functional compounds including alkalis and surfactants. These (A) polymerization systems are used as photoresist compositions for semiconductor etching. In particular, because it is less than 193 nm The low optical absorption is the primary characteristic of the material of the present invention, so it should have special utility at this wavelength. These polymers are not required at the wavelength of about 157 nanometers, but can have less than about 5.0 microns- Absorption coefficient of 1, typically at this wavelength Below about 4.0 microns M, and more typically, at this wavelength is less than about 35 microns_ 10 (A) Polymer: The fluorocopolymer (a) comprises a polymer derived from at least one ethylenically unsaturated compound The repeating unit is characterized in that the at least one ethylenically unsaturated compound is polycyclic. The copolymer is selected from the group consisting of: (al) a fluorinated copolymer comprising one derived from at least one ethylenically unsaturated compound A repeating unit, characterized in that at least one ethylenically unsaturated compound is polycyclic, and at least one other ethylenic unsaturated compound contains at least one fluorine atom, covalently attached to the ethylenically unsaturated carbon atom; and ( a2)-a fluorinated copolymer comprising repeating units derived from at least one polycyclic ethylenically unsaturated compound, the compound containing at least one fluorine atom, a perfluorinated group and a perfluorinated oxy group, which are co- Price connection-9-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

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k 591338 A7 B7 V. Description of the invention (6) to carbon atoms, this carbon atom system is contained in the ring structure, and each ethylenically unsaturated carbon atom of the ethylenic unsaturated compound is covalently formed by at least one The connected carbon atoms are separated. The at least one ethylenically unsaturated compound disclosed in (al) may be selected from the group consisting of:

(I) R11R12) a

(K)

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Among the lines: -10- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) A7 B7 ----- V. Description of the invention (7) Each m and n are 0, 丨 or 2, and p is An integer of at least 3; a and b are independently 1 to 3, but when b = 2, a is not = 1, or vice versa; R1 to Rb are all the same or different, and each represents a hydrogen atom, a halogen atom, Hydrocarbyl groups containing 1 to 14 carbon atoms, typically 1 to 10 carbon atoms, optionally substituted with at least one 0, N, S, P or halogen atom, such as several groups, such as secondary or tertiary alkyl groups Carboxylic acid group or carboxylic acid ester group; R1 5 is a saturated alkyl group of about 4 to 20 carbon atoms, and optionally contains one or more _ oxygen, with the proviso that the ratio of carbon atoms to hydrogen atoms is greater than or equal to 0.58; R16 to R21 are each independently a hydrogen atom, a C # C12 alkyl group, (CH ^ CC ^ A, C02 (CH2) q C02 A or C02 A, where q is 1 to 12, and A is a hydrogen or acid protecting group , With the proviso that at least one of Ri8 to R2 1 is C02 A. A key feature of the copolymer of the present invention (and the photoresist containing these copolymers) is that the polycyclic repeating unit is the same or different Fluorine repeating units' and furthermore, a synergistic combination with all repeating units that do not contain aromatic functional groups in the copolymer. In order to make the copolymer highly resistant to plasma etching (such as reactive ion etching), more The presence of cyclic repeating units in the copolymer is important. Polycyclic repeating units also tend to provide a high glass transition temperature, which is important for maintaining dimensional stability on the photoresist film. In order for the copolymer to have high Optical transparency, meaning low optical absorption in extreme and far UV, the existence of repeating units containing fluorine is very important. In order to make the polymer have high optical transparency, it is also necessary to avoid repeating units in the copolymer. Aromatic functional groups exist. -11-This paper size applies to China National Standards (CNS) Regulation 8 (21 ° father 297 mm) ----- 591338 A7 _____ B7 ___ V. Description of the invention (8) In certain embodiments of the present invention, the fluorinated copolymer may include repeating units derived from at least one polycyclic ethylenically unsaturated compound, the compound having at least one atom or group selected from the group consisting of fluorine atoms, Fluoroalkyl and perfluoroalkoxy groups are covalently attached to the carbon atoms contained in the ring structure. Fluorine, perfluorinated, and perfluorinated oxy, when such groups are directly connected to the vinyl system When unsaturated carbon atoms, it tends to inhibit the polymerization reaction of cyclic ethylenically unsaturated compounds by metal-catalyzed addition polymerization or metathesis polymerization. Therefore, in this case, it is important that the at least one fluorine atom, perfluoro Alkyl and perfluoroalkoxy are each ethylenically unsaturated carbon atom of an ethylenically unsaturated compound, separated by at least one carbon atom covalently connected. Furthermore, having this atom and / or group directly attached to the ring minimizes the presence of unwanted unfluorinated aliphatic carbon atoms. The copolymers of the present invention have surprisingly balanced properties, which is important for imparting the necessary properties &apos; to photoresist compositions for semiconductor applications. First, these copolymers have surprisingly low optical absorption in extreme and extreme UV, including 193 nm and 157 nm wavelengths. Making the copolymer with low optical absorption is very important for the deployment of high light speed photoresist. Most of the UV light is absorbed by the photoactive component and will not be lost by the copolymer (the substrate of the photoresist). . Secondly, the photoresist containing the fluorine-containing polymer of the present invention satisfactorily exhibits an extremely low plasma etching rate. The properties described later are important to obtain the high-resolution precision photoresistance required in semiconductor manufacturing. Achieving appropriate values for these properties at the same time is particularly important for imaging at 157 nm. In this case, it is necessary to exceed -12 · This paper size is applicable to China National Standard (CNS) A4 specification (21 × 297 mm) ~-Loading

591338 A7 B7 V. Description of the Invention (9) Thin photoresistors to provide high resolution, but these thin photoresists must be highly etch resistant so that the photoresist stays on the imaged substrate and protects the underlying substrate during etching Area of wood. In a preferred embodiment of the present invention, the photoresist composition comprises a copolymer comprising a comonomer derived from at least one polycyclic comonomer (that is, a comonomer comprising at least two rings, such as n-furene ) Of the repeating unit. This is important for three main reasons: 1) Polycyclic monomers have a relatively high carbon-to-hydrogen ratio (C: H), which can cause a base material consisting of repeating units of such polycyclic monomers Polymers, generally with good resistance to plasma etching; 2) Polymers with repeating units derived from polycyclic monomers, which are preferably fully saturated during polymerization, and generally have good transparency characteristics; And 3) Polymers made from polycyclic monomers often have relatively high glass transition temperatures to provide improved dimensional stability during processing. The ethylenically unsaturated group may be contained in a polycyclic partial group, such as in n-furene, or may be dangling to a polycyclic partial group, such as in vinyl 1-adamantanecarboxylate. Contains repeating units derived from polycyclic comonomers, a polymer with a high C: Η ratio, and a relatively low Ohnishi value (ON), where: ON = N / (NC-N0) where N is the polymer The number of atoms in the repeating unit, Ne is the number of carbon atoms in the repeating unit of the polymer, and N. Is the number of oxygen atoms in the polymer repeat unit. There is a rule of thumb discovered by Ohnishi et al. (J. Electrochem. Soc ·, Solid-State Sci · Technol "130, 143 (1983)), which states that the reactive ion etching (RIE) rate of the polymer is Ohnishi The linear function of the value (ON). Take the following as an example, poly (n-pinene) has the chemical formula -13- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm)

k 591338 A7 ______B7_ _ 5. The description of the invention (10) is poly (C7H10) and 0 · N · = 17/7 = 2.42. Polymers mainly composed of carbon and hydrogen, with polycyclic partial groups and relatively few oxygen-containing functional groups, have relatively low 0 · N ·, and according to the rule of thumb of OHhnishi, have a relatively low (in approximate In linear mode) RIE rate. As is known to those skilled in the art of polymer polymerization, ethylenically unsaturated compounds undergo radical polymerization to obtain polymers having repeating units derived from ethylenic unsaturated compounds. Specifically, an ethylenically unsaturated compound having the following structure undergoing a radical polymerization reaction:

To obtain a polymer with the following repeating units:

Among them, P, Q, S and T can be independently represented but not limited to η, F, Cl, Br, an alkyl group containing 1 to 14 carbon atoms, an aryl group containing 6 to 14 carbon atoms, an aralkyl group, or containing A cycloalkyl group of 3 to 14 carbon atoms. If only one type of ethylenically unsaturated compound is polymerized, the polymer formed is a homopolymer. If two or more different ethylenically unsaturated compounds are polymerized, the polymer formed is a copolymer. Some representative examples of ethylenically unsaturated compounds and their corresponding repeating units are shown below:

〆 \. W -14- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 591338 A7 B7 V. Description of the invention (11) Η \ C = C / Η

\ CH3 Η Η

, CH3

In the following paragraphs, the photoresist composition of the present invention is described from the viewpoint of its component parts. Binding

The photoresist of the present invention comprises a fluorinated copolymer comprising repeating units derived from at least one ethylenically unsaturated compound, characterized in that at least one ethylenic unsaturated compound is polycyclic and at least one ethylenic unsaturated The compound contains at least one fluorine atom and is covalently linked to an ethylenically unsaturated carbon atom. Representative ethylene-based unsaturated compounds suitable for the fluorinated copolymers of the present invention include, but are not limited to, tetrafluoroethane, trifluoroethylene, hexafluoropropylene, trifluoroethylene, difluoroethylene, vinyl fluoride, and perfluoro- (2,2-dimethyl-1,3-dioxin), perfluoro- (2.methylene methyl-1,3-dioxin), CF2 = CFO (CF2) tCF = CF2, where t is 1 or 2, and RfOCF == CF2, where Rf is a saturated fluoroalkyl group of 1 to about 10 carbon atoms. The fluorine-containing copolymer of the present invention may include any integer other gas-containing comonomer, including but not limited to those listed above. Preferred comonomers are tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, trifluoroethylene, and RfCF = CF2, where 1 ^ is a saturated fluoroalkyl group of 1 to about 10 carbon atoms. More preferred comonomers are tetrafluoroethylene, trifluoroethylene, hexafluoropropylene, and RfOCF = CF2, where Rf is a saturated perfluoroalkyl group of 1 to about 10 carbon atoms. The best comonomers are tetrafluoroethylene and chlorotrifluoroacetamidine. -15- This paper size is applicable to China National Standard (CNS) A4 (210X297mm) 591338 A7

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

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Line 591338 A7

Representative comonomers with structure M, including but not limited to:

All copolymers according to the invention comprising comonomers of the structures K, L and M are characterized by the inclusion of fluorinated olefins and vinyl ethers of the formula CH2 = CH02CR22 or vinyl ethers of the formula CH2 = CHOCH2R22 or ch2 = chor22 Type, where R22 is a hydrocarbon group of about 4 to 20 carbon atoms, where the ratio of c:: is relatively high, and its ratio is greater than 0.58, because the high C:: ratio is equivalent to good plasma etching resistance (this is related to the Women's hydrocarbons and vinyl esters of the formula CH2 = CH02 CR2 3, or copolymers of vinyl ethers of the formula CH2 = CHOCH2R23 or ch2 = chor23 are very different, in which R23 has a relatively low c: Η ratio, and is lower than 0.58. R22 and R23 are selected from the group consisting of alkyl, aryl, aralkyl, and cycloalkyl.) Representative comonomers having structure N, including but not limited to:

-17- ^ China National Standard (CNS) Α4 size for paper size 4 (210 X 297 mm)

Where A = H, (CH3) 3C, (〇 ^) 3Si. 'In the above-mentioned preferred embodiment, Qiaomaoren, T has at least one structure Η-Ν 的 ## is the second type of comonomer, if (and only if) fluorine-containing co- :: not included Other co-monomers selected from the group consisting of several acids and protected acid functional groups have restrictions on the first comonomer. In this case, the fluorinated copolymer has only two comonomers (two listed comonomers, and ^ has other unlisted comonomers). In this case, there must be a sufficient degree of ear energy, which is selected from the group consisting of carboxylic acids and protective acid groups, which are present in the at least one saturated compound (meaning the second listed comonomer), so that The photoresist of the present invention composed of a fluoropolymer can be developed during image copy exposure as explained in more detail below. In these specific examples using a fluorinated copolymer having only two comonomers, the mole percentages of the two comonomers in the copolymer are individually related to the fluoromonomer (the first listed Monomer) and the second co-monomer, which can range from 90% 10% to 10%, 90%. Typically, the percentage of these two comonomer moles, the individual parafluoro monomers (the first listed monomer) and the second comonomer, range from 60%, 40% to 40%, and 60%. Within range. For some specific embodiments, in addition to the two listed comonomers (that is, (i) at least one ethylenically unsaturated compound, containing at least one fluorine atom, covalently attached to the ethylenically unsaturated compound Saturated carbon atoms; and (H) at least one unsaturated compound selected from the group of structures HN), the fluorinated copolymer of the present invention may contain any integer without limitation other comonomers. Representative other comonomers may include, but are not limited to, acrylic acid and methyl 18. The paper size is applicable to Chinese National Standard (CNS) A4 specifications (210X 297 mm) B7 V. Description of the invention (15) Propionic acid, acrylic acid third _Butyl ester, tertiary butyl methacrylate, tertiary pentyl acrylate, tertiary pentyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethylene, vinyl acetate, decomposition Aconitic acid and vinyl alcohol. In a specific embodiment in which the fluorinated copolymer has two listed comonomers and includes two or more comonomers, the second listed comonomer (meaning ⑼ at least one unsaturated compound , Selected from the group h_n), which ranges from about 20 mole% to about 80 mole%, preferably from about 30 mole% to about 70 mole% ^ Mol%, and the best is ⑽ to about = ear%. The sum of the mole percentages of all other comonomers that make up this copolymer represents the balance, which adds up to 100% when added to the mole percentage of the second listed comonomer. The sum of the mole percentages of all other co-monomers present in the copolymer, except for the second listed comonomer &lt;, in a broad sense, is between about 80 mol% and about 20 mol%. Within range. The sum of the mole percentages of all other comonomers is preferably in the range of about 70 mole% to about 30 mole%. The sum of the mole percentages of all other comonomers is more preferably in the range of about 60 mole% to about 30 mole% 'and yet more preferably m. The sum of the mole percentages of all other comonomers is In the range of about 50 mole% to about 30 mole%. When this fluoropolymer is a terpolymer, the appropriate ratio of fluoro monomer (the first listed monomer @body) ^ ten other co-monomers, in short, can range from 5: = to 95 · 5. When this fluorinated copolymer has other comonomers having an acid group or a protected acid functional group in a sufficient amount necessary for imaging ability, the functional group may or may not be present in the second enumeration. Among the co-monomers, the limit is -19 591338 A7 B7 V. Description of the invention (16). A specific fluorinated copolymer of the photoresist composition of the present invention includes a repeating unit derived from a comonomer having at least one fluorine atom and connected to an ethylenically unsaturated carbon atom. The copolymer can be freely used. Made from radical polymerization. Polymers can be made by using bulk, solution, suspension, or emulsion polymerization techniques known to those skilled in the art, using free radical initiators such as azo compounds or peroxides. A specific fluorinated copolymer of the photoresist composition of the present invention, which contains only repeating units derived from all cyclic comonomers, and completely lacks unsaturated bonds derived from having one or more fluorine atoms connected to the ethylenic system. The repeating unit of comonomers of carbon atoms, the copolymer can also be made by free radical polymerization, but in addition, it can be made by other polymerization methods, including vinyl addition polymerization and ring opening metathesis polymerization (ROMP). Two polymerization methods described later are known to those skilled in the art. Vinyl addition polymerization using nickel and palladium catalysts is disclosed in the following references: 1) Okoroanyanwu U .; Shimokawa, T .; Byers, JD; Willson, CGJ Mol. Catal. A · Chemical 1998, 133, 93; 2) PCT WO 97/33198 (9/12/97) belongs to BF Goodrich; 3) Reinmuth, A .; Mathew, JP; Melia, J .;

Risse, W. Macromol. Rapid Commun. 1996, 17, 173; and 4) Breunig, S .; Risse, W. Makromol. Chem. 1992, 193, 2915. The ring-opening metathesis polymerization reaction system is disclosed in the references mentioned above. 1) and 2), using ruthenium and iridium catalysts; and 5) Schwab, P .; Grubbs, R. Η .; Ziller, JWJ Am. Chem. Soc. 1996, 118, 100: and 6) Schwab, P.; France, Μ. B .; Ziller, JW; Grubbs, RH Angew. Chem. Int. Ed. Engl. 1995, 34, 2039 -20- This paper size applies to the Chinese National Standard (CNS) A4 specification (210 x 297 mm)

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Line 591338 A7 B7 5. In the description of the invention (17), some of the fluorine-containing dimers of the photoresist composition of the present invention, wherein the dimer contains a fluorine-based monomer (such as TFE) and a cyclic olefin (such as n-pinene) , Which is shown as an alternating or approximately alternating dimer, which has, but is not limited to, the structure shown below:

In this case, the present invention includes such alternating or approximately alternating copolymers, but is not limited in any way to only alternating copolymer structures. These polymerization systems are described in WO 00/17712 published on March 20, 2000. The polymer (b) is a branched polymer containing a protected acid group, and the polymer contains one or more branched segments. , Chemically connected along the linear main chain. This branched polymer can be formed during radical addition polymerization of at least one ethylenically unsaturated macromonomer component and at least one ethylenically unsaturated comonomer. This ethylenically unsaturated macro component has a number average molecular weight (Mn) between hundreds and 40,000, and a linear main chain segment formed by a polymerization reaction, and has a number average molecular weight (Mn) between about 2,000 and about 500,000. between. The weight ratio of the linear main chain segment to the branch chain segment is in a range of about 50/1 to about 1/10, and preferably in a range of about 80/20 to about 60/40. Typically, the macromolecular component has a number average molecular weight (Mn) of from -500 to about 40,000, and more typically from about 1,000 to about 15,000. Typically, this type of ethylenically unsaturated macromolecular composition can have a number-average molecule -21-This paper size applies to China National Standard (CNS) A4 (210X 297 mm) binding

Line 591338 A7 B7 V. Description of the invention (18) The quantity (Mn) is equivalent to about 2 to about 500 monomer units, which are used to form macro-compositions, and are typically between 30 and 200 monomer units. In a typical embodiment, the branched polymer contains 25% to 100% by weight of a compatibility-promoting group, which means that the existence of these functional groups is to increase the compatibility with the photoacid generator. It is preferably about 50% to 100% by weight, and more preferably about 75% to 100% by weight. Suitable miscibility groups for ionic photoacid generators include, but are not limited to, non-hydrophilic polar groups and hydrophilic polar groups. Suitable non-hydrophilic polar radicals include, but are not limited to, cyano (-CN) and nitro (· ν02). Suitable hydrophilic polar groups include, but are not limited to, protic groups such as hydroxy (0Η), amine (ΝΗ2), ammonium, amido, amidoimine, carbamate, urea or thiol groups; or Chinic acid (C02), sulfonic acid, sulfinic acid, phosphoric acid or a salt thereof. The compatibility-promoting group is preferably present in the branched segment. Typically, protected acid groups (described below) generate acid acid groups after exposure to UV or other actinic radiation and subsequent post-exposure baking (meaning during a deprotection period). The branched polymer present in the photosensitive composition of the present invention typically contains a monomer unit containing a protected acid group at a ratio of about 3% to about 40% by weight, preferably about 5% to about Between about 50%, and more preferably between about 5% and about 20%. The branching segments of such preferred branched polymers typically contain between 35% and 100% of the protected acid groups present. Such branched polymers, when completely unprotected (all protected acid groups are converted into free acid groups), have an acid value between about 20 and about 500, preferably between about 30 and Between about 330, and more preferably between about 30 and about 130, and similarly, the ethylenically unsaturated macromolecular composition is better -22- This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) 591338 A7 B7 V. Description of the invention (19) It has an acid value between about 20 and about 650, more preferably between about 90 and about 300, and most of the free acid groups are in the branches In the chain. Each photosensitive composition of this aspect of the present invention contains a branched polymer, also called a comb-type polymer, which contains a protected acid group. This branched polymer has branched segments, called polymer arms, with a limited molecular weight and a limited weight ratio relative to the linear main segment. In a preferred embodiment, most of the protected acid groups are present in the branched segments. This composition also contains an ingredient, such as a photoacid generator, which makes the composition reactive to radiant energy, especially for radiant energy in the ultraviolet region of the electromagnetic spectrum, and most particularly in far or extreme ultraviolet Light area. In a specific embodiment, the branched polymerization system includes one or more branched segments that are chemically connected along a linear main segment, wherein the branched polymers have a number average molecular weight (Mn) of about 500. To 40,000. This branched polymer contains at least 0.5% by weight of branched segments. Branching segments, also known as polymer arms, are typically randomly distributed along a linear main chain segment. A "polymer arm" or branched segment is a polymer or oligomer of at least two repeating monomer units, which is connected to the linear main segment by a covalent bond. This branched segment or polymer arm can be incorporated into the branched polymer during the addition polymerization process of the macromonomer and the comonomer as a macromer component. For the purposes of the present invention, a "macro" is a polymer, copolymer or oligomer having a molecular weight ranging from several hundred to about 40,000, containing terminal ethylenically unsaturated and polymerizable groups. This giant is preferably a linear polymer or copolymer terminated with an ethylenic group. Typically, this branched polymer comes with one or -23- Chinese paper standard (CNS) A4 size (210 X 297 mm)

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591338 A7 B7 V. Description of the invention (20) A copolymer of a plurality of polymer arms, and preferably at least two polymer arms, which is characterized by being between about 0.5 and about 80% by weight, preferably about The monomer components used in the polymerization method between 5 and 50% by weight are giants. Typically, along with the comonomer component of the macromolecule used in the polymerization method, it also contains a single ethylenic group, which can be copolymerized with ethylenically unsaturated macromonomers. The ethylenically unsaturated 1 depleted body, and the branched segments and / or the main chain of the branched polymer formed, may have one or more protected acid groups bonded thereto. For the purposes of the present invention, a `` protected acid group '' means a functional group that, upon removal of the protection, will obtain a free acid functional group that will strengthen the macrosome and / or the branched form to which it is bound The solubility, swelling or dispersing ability of polymers in aqueous environments. Protected acid groups can be incorporated into the branched segments and / or branched polymers of the ethylenically unsaturated macrosomes and the branched polymers formed. In the main chain, whether it is during or after its formation. 0 Although the addition polymerization of a macro and at least one ethylenically unsaturated monomer is used, it is preferable to form a branched polymer, but the use of either All known methods for addition or condensation reactions to prepare branched polymers can be used in the present invention. Furthermore, the use of both pre-formed main chains and branched segments The on-site polymerization segment can also be applied in the present invention. The branch segment connected to the linear main segment can be derived from an ethylene-based unsaturated giant, which is based on one of US Patent 4,680,352 and US Patent 4,694,054-generally The description is made. The giant system is made by free radical polymerization method, using cobalt compound as the catalytic chain transfer agent, and especially the auspicious compound. Lead (II) -24- The dimensions of this paper are applicable to Chinese National Standard (CNS) A4 Specifications (210 x 297 mm)

Jingling

Line 591338 A7 B7 V. Description of the invention (21 The compound may be a pentacyanocobalt (II) compound, or a chelate compound of the following compounds, a iminohydroxyimino compound, a dihydroxyimino compound, two Azadihydroxyimidodialkyldecadiene, diazadihydroxyimido-dialkylfluorene-fluorenediene, tetraazatetracyclocyclotetradecane tetraene, tetraazatetracyclocyclododecane Alkyl tetraene, bis (difluoroboryl) diphenylglyoxal, bis (difluoroboryl) dimethylglyoxal M group, Ν, Ν'-bis (sialylene) Ethylenediamine, dialkyldiaza-dioxodialkyldodecadiene or dialkyldiazodioxydialkyl-tridecadiene. Low molecular weight methylpropionate It can also be made from a pentacyano cobalt (II) catalyzed chain transfer agent, as disclosed in U.S. Patent No. 4,722,984. An illustrative giant using this approach is methacrylic acid with an acrylate or other vinyl monomer Ester polymer, in which the polymer or copolymer has a terminal ethylenic group and a hydrophilic functional group. The preferred monomer component for preparing macromers, including : Third-butyl methacrylate (tBMA), third-butyl acrylate (tBA), methyl methacrylate (MMA); ethyl methacrylate (EMA); butyl methacrylate (BMA); 2-ethylhexyl methacrylate; methyl acrylate (MA); ethyl acrylate (EA); butyl acrylate (BA); 2-ethylhexyl acrylate; 2-hydroxyethyl methacrylate (HEMA) ; 2-hydroxyethyl acrylate (HEA); methacrylic acid (MA); acrylic acid (AA); esters of acrylic acid and methacrylic acid, in which the ester group contains 1 to 18 carbon atoms; acrylic acid and methacrylic acid Nitriles and amidines (such as acrylonitrile); glycidyl esters of methacrylic acid and acrylic acid; decomposition of aconitic acid (IA) and decomposition of aconitic acid-anhydride (ITA), half esters, and iminoimides; maleic acid Acid and maleic anhydride, half-esters and fluorene imines; aminoethyl methacrylate; third methacrylic acid-25- This paper size applies to China National Standard (CNS) A4 (210X297 mm)

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V. Description of the invention (22) Butylaminoethyl; dimethylaminoethyl methacrylate; monoethylaminoethyl methacrylate; ethylaminoethyl acrylate; dimethylaminoethyl valerate Esters; diethylaminoethyl acrylate; acrylamide; ammonium tertiary-octylacrylamide; vinyl methyl ether; styrene (STY); α-methylstyrene (AMS); vinyl acetate; Vinyl chloride, etc. Decomposition aconitic anhydride (ΙΤΑ, 2-methylene succinic acid, CAS number = 217〇-〇3-8) is a particularly advantageous comonomer for branched polymers, because it has two reactive functional groups, In the form of anhydride, it becomes three kinds when ring-opening. The ethylenically unsaturated group is the first functional group, which provides the ability of this comonomer to be incorporated into the copolymer, such as by free radical polymerization. The anhydride moiety is a second functional group that can react with a variety of other functional groups to obtain a covalently bonded product. An example of a functional group with which a molybdenum group can react is a radical in an alcohol to form an ester chain. When the anhydride group of ITA reacts with a hydroxyl group, it forms an ester chain, and the free-state carboxylic acid group is a third functional group. This carboxylic acid functional group can be used to impart aqueous solution processing properties to the photoresist of the present invention. If a PAG with a hydroxyl group is used, as shown in some examples, it can be covalently bonded to the PAG (or other photoactive species) via an ester link (or other covalent link such as amidine, etc.) of this type. Ingredients) are linked (tethered) to branched polymers containing ITA co-monomers or their analogs. This branched polymer can be made by any conventional addition polymerization method. This branched polymer or comb-type polymer can be made from one or more compatible ethylenically unsaturated macromonomer components and one or more compatible conventional ethylenically unsaturated comonomer components. Addition-polymerizable ethylenically unsaturated co-monomers

k order

Line -26-

591338 A7 B7 V. Description of the invention (23) The body composition is propionate, methacrylate, phenylethylene, and mixtures thereof. Appropriate addition-polymerizable ethylenically unsaturated comonomer components, including: tertiary butyl methacrylate (tBMA), tertiary butyl acrylate (tBA), methyl methacrylate (MMA); methyl Ethyl Acrylate (EMA); Butyl Methacrylate (BMA); 2-ethylhexyl Methacrylate; Methyl Acrylate (MA); Ethyl Acrylate (EA); Butyl Acrylate (BA); Ethylhexyl Ester; 2-Hydroxyethyl Methacrylate (HEMA); 2- # to Ethyl Acrylate (HEA); Methacrylic Acid (MAA); Acrylic Acid (AA); Acrylonitrile (AN); Methyl Ester Acrylonitrile (MAN); Decomposing aconitic acid (ΙΑ), and decomposing aconitic acid (ΙΑΑ), half esters, and fluorimides; maleic acid, and maleic acid, halides, and imines; Aminoethyl methacrylate; third methacrylic acid; butylaminoethyl methacrylate; dimethylaminoethyl methacrylate; diethylaminoethyl methacrylate; aminoethyl acrylate; acrylic acid Dimethylaminoethyl; Diethylaminoethyl Acrylate; Acrylamide; N-Third-octylpropylamine; Vinyl methyl ethers; Styrene (S); α • methyl Phenyl Ethylene Esters; Most copolymerizable monomers must be acrylic or styrenic or copolymers of these monomers with acrylates and other vinyl monomers. Each component of the branched polymer of the present invention has a linear main chain segment and / or a branched chain segment, and may contain various functional groups. "Functional group" is considered to be able to be connected to the main segment or branch segment (any part of the group by a direct h bond or by a linking group. It can be the main segment or the branch segment An illustrative example of the functional group — is -COOR24; _〇R24; · 5 {124, where R24 can be a hydrogen 'alkyl group having 1 to 12 carbon atoms; a cycloalkane having 3 to 12 carbon atoms -27- 591338

An aryl, alkaryl or aralkyl group having 6 to 14 carbon atoms; a heterocyclic group containing 3 to 12 carbon atoms and additionally containing at least one s, 0, N or p atom; or -OR27, where R27 can be an alkyl group of M2 carbon atoms, an aryl, alkaryl or arylfluorenyl group having 6 to 14 carbon atoms; CN; -NR25R26, or -c-nr25r26 where R2) and R26 May be hydrogen, alkyl having i to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; aryl, alkaryl, aralkyl having 6 to 14 carbon atoms; -CH2 OR2 8, Wherein r2 8 is hydrogen, an alkyl group of j to 12 carbon atoms; or a ring alkyl group of 3 to 12 carbon atoms, an aryl group, alkylaryl group, aralkyl group, or transalkyl group having 6 to 14 carbon atoms. And trans ^ can form a heterocyclic ring having 3 to 12 carbon atoms and containing at least one s, N, 0 or p; .Γ · —g = cr30r31 where R2 9, Rj 0 and R31 can be hydrogen, 1 to An alkyl group of 12 carbon atoms, or a cyclofluorenyl group of 3.12 carbon atoms; an aryl group, an arylene group, an aralkyl group of 6 to 14 carbon atoms, or -COOR24, or when R29, R3〇, and / When used together with R31, it can form a cyclic group; -SC ^ H; Urethane group; Isocyanate or blocked isocyanate group; Urea group; Ethylene oxide group; Azido group; Squindiazide group; Azo group; Azide -Diazo; ethenylacetoxy; -SiR32R33R34, where R32, R33 &amp; R34 may be an alkyl group having M2 carbon atoms, or a cycloalkyl group having 3-12 carbon atoms, or. -28 -This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 X 297 mm) 591338 A7 ______B7 5. Description of the invention (25) OR, where R3 5 is an alkyl group of 1-12 carbon atoms, or 3-12 Cycloalkyl of 6 carbon atoms; aryl, alkaryl or aralkyl of 6 to 14 carbon atoms; or r36, · SRWRW or -N + R36R37R38 group (where r36, r37 and r38 can be hydrogen, an alkyl group of 1 to 12 carbon atoms, or a cycloalkyl group of 12 carbon atoms; 6 to 14 carbon atoms Aryl, alkaryl or aralkyl; or any of the foregoing salts or complex salts. Preferred functional groups are -C00N, -0H, -Nh2, amido, vinyl, urethane, isocyanate Blocked isocyanide An ester group, or a combination thereof. The functional group may be located anywhere on the branched polymer. However, 'sometimes it is necessary to select a comonomer that gives the overall polymer characteristics to the linear main segment of the branched polymer, and In addition to hydrophilicity, macros that impart physical and chemical functionalities to branched segments, such as solubility and reactivity. In certain preferred embodiments of the present invention, the branched polymer contains a functional group compatible with the photoacid generator, and the functional group is distributed in the branched polymer such that 25 to 100% The functional group is present in the segment of the branched polymer containing most of the protected acid groups. These functional groups are satisfactory because photoacid generators have enhanced compatibility with branched polymer segments with most protected acid groups, resulting in higher light speeds and possible higher resolution Degrees, and / or other desirable properties of photoresists, which include branched polymers having such functional groups to promote compatibility. For ionic PAGs, such as triarylsulfonium salts, functional groups that promote compatibility include, but are not limited to, polar non-hydrophilic groups (such as nitro or cyano) and polar hydrophilic groups (such as Junji). For non--29- this paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 591338

Ionic PAGs, such as the structure m below, are preferred functional groups for imparting compatibility and are of a lower polarity than the polar groups listed above. In the latter case, the &apos; appropriate functional group includes, but is not limited to, groups which impart fairly similar chemical and physical properties to non-ionic circles. Taking the following as two specific examples, aromatic and perfluoroalkyl functional groups are effective to promote the compatibility of branched polymers with non-ionic PAGs (such as the structure shown below). In some preferred embodiments, the branched polymer is an acrylic acid / methacrylic acid / styrenic copolymer, which is at least 60% by weight acrylic acid, and has at least 60% methacrylic acid. A repeating unit exists in either the first position or the second position. The first position is one of the segments (meaning a branch segment or a linear main segment), and the second position is the same as the first position. Segments with different positions where at least 60% of the acrylate repeat units are present at the second position. In some embodiments, the branched polymer is a fluorine-containing graft copolymer that includes repeating units derived from at least one ethylenically unsaturated compound, the compound containing at least one fluorine atom, covalently linked to Ethylene is an unsaturated carbon atom. The repeating unit having at least one fluorine atom may be either in the main segment of the linear polymer or in the branched polymer segment; it is preferably in the main segment of the linear polymer. Representative ethylene-based unsaturated compounds suitable for the fluorine-containing graft copolymers of the present invention include, but are not limited to, tetrafluoroethylene, chlorotrifluoroethane, hexafluoropropylene, trifluoroacetamidine, difluoroethylene, vinyl fluoride, and RfOCF = CF2, where Rf is a saturated perfluoroalkyl group of 1 to about 10-carbon atoms. The fluorinated copolymer of the present invention may contain any integer other fluorinated co-monomers, including but not limited to those listed above. -30- This paper size applies to China National Standard (CNS) A4 specifications (210X 297 mm) 591338 A7 B7 V. Description of the invention (shown in 27. Preferred comonomers are tetrafluoroethylene, trifluoroethylene, hexafluoropropylene, trifluoroethylene, and Rf0CF = CF2, with the center of 丄 to about ι0 carbon atoms. Saturated perfluoroalkyl. More preferred comonomers are tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and RfCF = CF2, where ~ is a saturated perfluoroalkyl group of about 10 to about 10 carbon atoms. Best The comonomers are tetrafluoroethylene and chlorotrifluoroethylene. In some preferred embodiments, the fluorine-containing graft copolymer further comprises repeating units derived from at least one unsaturated compound, selected from the group consisting of the above polymers ( The structure shown in a). In a specific embodiment of the present invention, pAG is connected to the fluorine-containing graft copolymer in a covalent bond manner (that is, is retained), and photoresist is obtained. In some preferred embodiments, In embodiments, the branched polymer is a fluorinated copolymer, which includes One kind of unsaturated associative acetate repeating units of compounds, the fluoro compound-containing alcohol functional group, having the structure:

-C (Rf) (Rf,) OH with the same or different fluoroalkyl group having 1 to about 10 carbon atoms at the center, or taken together as (CF2) n, where η is 2 to 10. A specific fluorine-containing branched copolymer according to the present invention, which comprises repeating units derived from at least one ethylenically unsaturated compound containing a fluoroalcohol functional group. The copolymer may have a fluoroalkyl group as a fluoroalcohol A part of Guan Yeji. These fluoroalkyl systems are referred to as amines, and they can be partially fluorinated alkyls or fully fluorinated alkyls (meaning perfluoroalkyls). Broadly speaking, Rf and Rf are the same or different fluoroalkyl groups of 1 to about ί carbon atoms, or are used together as (CF2) n, where n is 2 to 10 (in this last sentence, "used together • 'The term refers to heart and Rf. It is not an individual, discontinuous fluorinated alkyl group, but -31-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

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To form a ring structure, as shown in the following 5-member ring case:

According to this issue, Rf and Rf · can be partially fluorinated groups without limitation, but there must be sufficient degree of fluorination to impart acidity to the hydroxyl group (· 〇Η) of the fluoroalcohol functional group, so that the hydroxyl group The proton system is substantially removed in an alkaline medium, such as in an aqueous solution of sodium hydroxide or an aqueous solution of tetraalkylammonium hydroxide. In the preferred case according to the present invention, there is sufficient fluorine substitution in the fluorinated alkyl group of the fluoroalcohol T-energy group, so that the hydroxyl group has a pKa value of 5 &lt; pKa &lt; 11. Rf and Rf are preferably perfluoroalkyl groups having 1 to 5 carbon atoms independently, and Rf and Rf are most preferably trifluoromethyl (CF3). Each fluorinated copolymer according to the present invention preferably has an absorption coefficient of less than 4.0 microns-1 at a wavelength of 157 nm, and preferably less than 35 microns · 1 at this wavelength, and more preferably It is below 30 μm-i at this wavelength. The fluorinated polymer, photoresist and method of the present invention containing a fluoroalcohol functional group may have the following structure:

-ZCH2C (Rf) (Rf,) 〇H where Rf and Rf · are the same or different fluoroalkyl groups of 1 to about 10 carbon atoms, or used together as (CF2) n, where n is 2 to 10; z It is selected from the group consisting of oxygen, osmium, nitrogen, phosphorus, other VA group elements, and other v! A group elements. So-called, other VA group elements, and the terms of "other group elements", should be clear that these terms-as used herein, refer to any other element in one of these groups of the periodic table that is not in this group Listed elements (meaning oxygen, sulfur, nitrogen, phosphorus). -32- This paper size is in accordance with Chinese National Standard (CNS) A4 (21 × 297 mm) 591338 A7 B7 V. Description of the invention (29 oxygen is the preferred Z group. It contains a fluoroalcohol functional group and is in the present invention Some illustrative but non-limiting examples of representative comonomers within the scope are set out below:

j ^ J-CH2C (CF3) 2〇Hj ^ J-CH2〇CH2C (CF3) 2〇H

CH2 = CHOCH2CH2〇CH2C (CF3) 2OH · ch2 = cho (ch2) 4och2c (cf3) 2oh As is well known to those skilled in the art of polymer polymerization, ethylenically unsaturated compounds undergo radical polymerization to obtain derivatives derived from Polymers of repeating units of unsaturated compounds. Specifically, the acetamidine unsaturated compound having the following structure:

Q

It is as described above with respect to the copolymer (al). A fluoropolymer having at least one fluoroalcohol group is selected from the group consisting of: (cl) a fluoropolymer containing repeating units derived from at least one ethylenically unsaturated compound, the compound containing a fluoroalcohol functional group , Has the following structure: -33- This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) 591338 Description of the invention

-C (Rf) (Rf,) 〇H wherein Rf and Rf are as described above; (c2) a fluorinated copolymer comprising repeating units derived from at least one ethylenically unsaturated compound, characterized by at least one Ethylene unsaturated compounds are cyclic or polycyclic, at least one ethylenically unsaturated compound contains at least one fluorine atom, is covalently connected to an ethylenically unsaturated carbon atom, and at least one ethylenically unsaturated compound contains The fluoroalcohol functional group has the following structure ...

-C (Rf) (Rf,) 〇H wherein Rf and Rf are as described above; (c3) a fluorinated copolymer comprising: (0 repeating units derived from at least one ethylenically unsaturated compound 'the compound Contains at least three fluorine atoms, covalently connected to two ethylenically unsaturated carbon atoms; and (ii) a repeating unit derived from an ethylenically unsaturated compound, which contains a fluoroalcohol functional group, and has the following structure:

-C (Rf) (Rf,) OH where Rf and Rf are both as described above; (c4) a fluorinated copolymer comprising repeating units derived from at least one ethylenically unsaturated compound containing a fluoroalcohol function Base with the following structure:

-ZCH2C (Rf) (Rf,) OH wherein Rf and Rf are as described above; and Z is an element selected from the VA group and other groups of the periodic table (CAS version). Typically, χ is sulfur, oxygen, 34- This paper size applies to China National Standard (CNS) A4 specifications (210X 297 mm)

Hold

591338 A7 B7 V. Description of the invention (31) Nitrogen or phosphorus atom; (c5) A fluorine-containing polymer, which contains the following structure:

Each of R40, RC, trans 42 and # 3 is independently a hydrogen atom, and the atom containing a hydrocarbon group of 1 to 10 carbon atoms is substituted with at least one 0, s, N, p or halogen and has! Hydrocarbyl groups of up to 12 carbon atoms, such as alkoxy, carboxylic acid, carboxylate, or functional groups containing the following structure ...

Line-C (Rf) (Rf,) OR44 where Rf and Rf are as described above; r4 4 is a hydrogen atom, or an acid-or labile-unstable protecting group; v is the number of repeating units in the polymer; ~ is 〇4; at least one repeating unit has a structure in which at least one R4 〇, R4 1, R42 and R43 contain the structure C (Rf) (Rf,) OR44, for example R40, R41 &amp; R42 is a hydrogen atom, and R43 is ch2och2c ( cf3) 2och2co2c (ch3) 3, where CH2C02C (CH3) 3 is an acid or base labile protecting group, or R43 is och2c (cf3) 2och2co2c (ch3) 3, where 0CH2C02C (CH3) 3 is an acid or base labile protecting group ; And (C6) — a type of polymer comprising: (i) a repeating sheet derived from at least one ethylenically unsaturated compound-35- This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) 591338 A7 B7

Position, the compound contains a fluoroalcohol functional group, and has the following structure--C (Rf) (Rf,) 0H wherein Rf and Rf · are as described above; and ⑻ is derived from at least one ethylenically unsaturated group having the following structure Compound repeating unit: (h) (r45) 〇c (r46) (cn) where R45 is a hydrogen atom or CN; 1146 is a (: 1-(: 8 alkyl group, hydrogen atom or a c02R47 group, where is Ci-C8 alkyl or hydrogen. This fluoropolymer or copolymer contains repeating units (discussed below) derived from at least one ethylenically unsaturated compound, which contains a fluoroalcohol functional group, which may have a fluoroalkyl group. Exists, as part of the fluoroalcohol group, and is described above with respect to the copolymer (b). These fluoroalkyl groups are referred to as Rf and Rf as described above. As is known to those skilled in polymer arts, B The associated unsaturated compound undergoes a radical polymerization reaction to obtain a polymer having a repeating unit derived from an ethylenic unsaturated compound. Specifically, the ethylenically unsaturated compound has the following structure:

Is described above with respect to the copolymer (al). Each fluorinated copolymer according to the present invention has the paper size at a wavelength of 157 nanometers and is applicable to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 591338 A7 B7 5. Description of the invention (33) Low absorption coefficient At 4.0 microns-1, it is preferably below 3.5 microns-1 'at this wavelength, more preferably below 3.0 microns1' at this wavelength, and more preferably below 2.5 microns_1 at this wavelength. The fluorinated polymer, photoresist and method of the present invention containing a fluoroalcohol functional group may have the following structure:

-ZCH2C (Rf) (Rf,) OH wherein Rf and Rf are as described above; Z is as described above. Some illustrative but non-limiting examples of representative comonomers that contain fluoroalcohol functionality and are within the scope of the present invention are set out below:

CH2C (CF3) 2〇H

CH20CH2C (CF3) 20H

ch2c (cf3) 2oh

CH20CH2C (CF3) 20H

CH2 = CHOCH2CH2OCH2C (CF3) 2OH CH2 = CHO (CH 2) 4OCH 2C (CF 3) 2OH

〇 一 CH2〇 (CF3) 2〇H 〇ch2c (cf3) 20h Various bifunctional compounds that can initially provide cross-linking and subsequent cleavage (for example, when exposed to strong acids), can also be used in the copolymers of the present invention Used as a comonomer. As an illustrative but non-limiting example, the bifunctional comonomer NB-F-OMOMO-F-NB is satisfactorily used in the copolymers of the present invention as a total of -37. The paper size applies to Chinese National Standard (CNS) A4 Specifications (210 X 297 mm) 591338 A7 B7 5. Description of the invention (34) monomer. When it is similar to the dual-T-functional comonomer, when present in the copolymer component of the photoresist composition of the present invention, a copolymer can be obtained, which is a material with a relatively high molecular weight and a slight X-linkage. Photoresist compositions incorporating such copolymers containing bifunctional monomers may have improved imaging and imaging characteristics due to exposure to light (which produces a strong acid photochemically, as explained below), which Factors that cause bifunctional group splitting, and therefore a significant reduction in molecular weight, can provide greatly improved imaging and imaging characteristics (eg, improved contrast). These fluoroalcohol groups and their specific examples are more detailed as described above and in PCT / US00 / 11539, filed on April 28, 2000. At least a portion of the nitrile functional groups present in the nitrile / fluoroalcohol polymer are caused by the incorporation of repeating units derived from at least one ethylenically unsaturated compound. The side compound has at least one nitrile group and has the following structure (H) (R48) C = C (R49) (CN) where R48 is a hydrogen atom or a cyano group (CN); R4 9 is an alkyl group ranging from i to about 8 carbon atoms, and the C02R50 group Wherein R50 is an alkyl group ranging from about 8 carbon atoms, or a hydrogen atom. Acrylonitrile, methacrylonitrile, transbutadionitrile (trans-1,2-dicyanoethylene), and cis-butadionitrile (cis-, 2-dicyanoethylene) are preferred. Acrylonitrile is the best. Yueyue / fluoroalcohol polymers are typically characterized by having repeating units derived from at least one ethylenically unsaturated compound, which contain fluoroalcohol functional groups, which are present in the nitrile / fluoroalcohol polymer, from about 10 to about 6 〇Moore percentage, and repeating units derived from at least one ethylenically unsaturated compound, which are -38- This paper size applies to China National Standard (CNS) A4 (210X297 mm)

Binding

▲ 591338 A7 B7 5. Description of the invention (35) Contains at least one nitrile group present in the polymer, about 20 to about 80 mole percent. More typically for nitrile / fluoroalcohol polymers that achieve low absorption coefficient values, it is characterized by having repeating units derived from at least one ethylenically unsaturated compound, which contains a fluoroalcohol functional group, at a level of 45 or less The mole percentage is present in the polymer, and is more typically less than or equal to 30 mole percentage, and has a relatively small amount of repeating units containing nitrile groups, resulting in at least a portion of the polymer's balance. In a specific embodiment, the polymer comprises at least one protected functional group. The functional group of the at least one protected functional group is typically selected from the group consisting of an acidic functional group and a basic functional group. Non-limiting examples of protected functional groups are carboxylic acids and fluoroalcohols. In another embodiment, the nitrile / fluoroalcohol polymer may include an aliphatic polycyclic functional group. In this specific embodiment, the percentage of repeating units of the nitrile / fluoroalcohol polymer containing aliphatic polycyclic functional groups ranges from about 1 to about 70, preferably about 10 to about 55 mole%; and A more typical range is from about 20 to about 45 mole%. Except where explicitly stated and referred to herein, this nitrile / fluoroalcohol polymer may contain other functional groups with the proviso that the aromatic functional group is preferably not present in the nitrile / fluoroalcohol polymer. The presence of aromatic functional groups in these polymers has been found to detract from their transparency and cause them to absorb too strongly in the far and extreme UV regions, making them unsuitable for use in layers imaged at these wavelengths. In some specific embodiments, the polymerization system is a branched polymer, which includes one or more branched segments, which are chemically connected along the linear main chain segment -39-This paper applies Chinese National Standards (CNS) A4 size (210X 297 mm)

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Pick up. This branched polymer can be formed during the radical addition polymerization of at least one ethylene-based unsaturated macromonomer and at least one ethylene-based unsaturated comonomer. This branched polymer can be made by any conventional addition polymerization method. ° This branched polymer or comb-shaped polymer can be made from one or more phase-unsaturated ethylenically unsaturated macro-components, and one or more Compatible customary ethylenic unsaturated macro-components and one or more compatible customary ethylenic unsaturated monomer components. Typically, the addition-polymerizable ethylenically unsaturated monomers are acrylonitrile, methacrylonitrile, fumaronitrile, cis-butadiene-nitrile, and protected and / or unprotected unsaturated fluoro groups. Alcohols,. Dibao and / or unprotected unsaturated carboxylic acids. The structure and method of making this type of branched polymer is discussed with respect to the polymer type (b) above and as described in WO 00/25178. A fluoropolymer having at least one fluoroalcohol, which may further include a spacer group, selected from the group consisting of ethylene, α · olefins, 1, Γ-disubstituted olefins, ethynyl alcohols, vinyl ethers, and 1,3-bis Olefins. Polymer (d) includes perfluoro (2,2-dimethyl-1,3-dioxolene) or CX2 = CY2 amorphous vinyl homopolymer, where X = f or CF3, and Υ = -Η, or perfluoro (2,2-dimethyl-1,3-dioxolene) and CX2 = CY2i amorphous ethylenic copolymer, the homopolymer or copolymer contains one or A variety of comonomers CR51R52 = CR53R54, where each R51, R52, R53 is independently selected from Η or F, and where R54 is selected from the group consisting of -F, -CF3, -OR55, where R55 is CnF2n + l, where 1 to 3 , -OH (when r53 = h) and Cl (when R5 1, R52 and R53 = F). Aggregate can additionally contain CH2 = CHCF3 and CF2 = CF2, with a ratio of 1: 2 to 2: 1, CH2 = CHF and CF2 = CFC1, with -40- This paper size applies to China National Standard (CNS) A4 specifications (210X (297 mm)

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Line 591338 A7 B7 V. Description of the invention (37) 1: 2 to 2: 1 ratio, CH2 = CHF and CC1H = CF2, at a ratio of 1: 2 to 2: 1, perfluoro 1,3-dioxolane) in any ratio with perfluoro (2,2-dimethyl-1,3-dioxolene), perfluoro (2-methylene-4-methyl-1 , 3-dioxolane) is an amorphous vinyl copolymer with difluoroethylene in any ratio, which is amorphous, and perfluoro (2-methylene ice methyl-1,3-dioxolane) Ii) homopolymer. These polymerization systems are made by polymerization methods known in the art about fluoropolymers. All these polymers can be made by sealing monomers, inert fluids (such as CF2C1CC12F, CF3CFHCFHCF2CF3, or carbon dioxide) and soluble free-radical initiators, such as HFPO dimer peroxide L or Perkadox® 16N, in a sealed In a cooled autoclave, then heat as appropriate to initiate polymerization. CF3 CF2 CF2 OCF (CF3) (C = 0) 00 (C = 0) CF (CF3) OCF2 CF2CF3 1 For HFPO dimer peroxide L, room temperature (~ 25 ° C) is a suitable polymerization reaction temperature For Perkadox®, a temperature of 60 to 90 ° C can be used. Depending on the monomer and polymerization temperature, the pressure can be changed from atmospheric to 500 psi or higher. Then, when the polymer is formed as an insoluble precipitate, it can be separated by filtration, or when it is soluble in the reaction mixture, it can be separated by evaporation or precipitation. In many cases, apparently dried polymers still retain considerable solvents and / or unreacted monomers and must be further dried in a vacuum oven, preferably under nitrogen flow. Many polymers can also be made by aqueous emulsion polymerization, which is achieved in the following way. Deionized water, initiators such as ammonium persulfate or Vazo®56 WSP, monomers, -41-This paper size applies Chinese national standards (CNS) A4 size (210 X 297 mm)

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591338 A7 _______ B7_ V. Description of the Invention (38) A surfactant such as ammonium perfluorooctanoate or a dispersant such as methyl cellulose is sealed in a cooling autoclave and heated to initiate a polymerization reaction. This polymer can be separated by crushing, filtering and drying any emulsion formed. In all cases, oxygen should be excluded from the reaction mixture. A chain transfer agent such as chloroform may be added to reduce the molecular weight. Nitrile / fluoroalcohol-containing polymers (e) made from substituted or unsubstituted ethylene ethers, comprising: (el)-a polymer comprising: (i) surviving from at least one type Is a repeating unit of an unsaturated compound. This compound contains a vinyl ether functional group and has the following structure: CH2 = CH〇.R56 where R56 is an alkyl group having 1 to 2 carbon atoms and 6 to about 20 carbon atoms Aryl, aralkyl or alkaryl, or the group is substituted with at least one S, 0, N or P atom; and (ii) a repeat derived from at least one ethylenically unsaturated compound having the structure Unit: (H) (R57) C = C (R58) (CN) where R? 7 is a hydrogen atom or a cyano group; R5 8 is a pit group ranging from 丨 to about 8 carbon atoms, C02 R5 9, where R5 9 is an alkyl 'or hydrogen atom ranging from i to about 8 carbon atoms; and (iii) a repeating unit derived from at least one ethylenically unsaturated compound containing an acidic group; and (e2) a polymer, It contains ·· -42- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 591338 A7 ___ B7 V. Description of the invention (39) (i) A repeating unit derived from at least one ethylenically unsaturated compound containing a vinyl ether functional group and a fluoroalcohol functional group and having the following structure:

C (R6 〇XR6 1 H: (r6 2 &gt; 〇_DC (Rf) (Rf,) 〇H where R, r6 1 and r6 2 are independently hydrogen atoms, ranging from i to about 3 carbon atoms of alkane D is at least one atom, which is connected to the ethyl atom ether functional group through the oxygen atom to the carbon atom of the isopropyl alcohol group, Rf and Rf, as described above; and ⑻ is derived from at least one of the following structures Repeating units of ethylenically unsaturated compounds: (h) (r57) c = c (r58) (cn) where R57 is a hydrogen atom or a cyano group; R58 is an alkyl group ranging from i to about 8 carbon atoms' C 〇2 R5 9 groups, wherein 9 is an alkyl group, or a hydrogen atom, ranging from 1 to about 8 carbon atoms; and (iii) a repeating unit derived from at least one ethylenically unsaturated compound containing an acidic group. This fluoroalcohol group and specific examples are described in more detail with respect to the polymer (c6) above. It is included in the general structural formula (previously described) containing an amino alcohol group and is within the scope of the present invention. Some illustrative but non-limiting examples of vinyl ether monomers are presented below: ch2 = choch2 ch2 och2 C (CF3) 2 OH ch2 = CHO (CH2) 4 〇ch2 C ( CF3) 2 OH nitrile group and specific examples thereof, and linear and branched polymers made of nitrile and fluoroalcohol groups, and specific examples thereof, and also for the polymer (c6) above in more detail Describe and quote. -43- $ Paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) '591338 A7 B7 V. Description of the invention (4〇

These polymers may be present in an amount of about 10 to about 99.5% by weight based on the weight of the entire composition (solid). iLj tongue component ΠΜρ If the polymer in the polymer blend is not photoactive, the composition of the present invention may contain a photoactive component (PAC), which is not chemically bound to the fluoropolymer, meaning That is, the photoactive ingredients are individual ingredients in the composition. Photoactive ingredients are compounds which, whether exposed to actinic radiation, can be acidic or alkaline. If the acid system is generated when exposed to actinic radiation, the PAC system is called a photoacid generator (PAG). If the alkali system is generated when exposed to actinic radiation, the PAC system is called a photobase generator (PBG). Suitable photoacid generators for use in the present invention include, but are not limited to,) phosphonium salts (Structure I), 2) iodonium salts (Structure II), and 3) hydroxamates, such as Structure III.

Order

In structures I-II, Ri-R3 is independently a substituted or unsubstituted aryl group, or a substituted or unsubstituted Ci-C ^ oalkylaryl group (aralkyl). Representative aryl groups include, but are not limited to, phenyl and fluorenyl. Appropriate substituents include, but are not limited to, hydroxyalkoxy (for example, the anion σ of c10h21c ^ in structure I-II, which may be, but not limited to, SbF6- (hexafluoroantimonate), -44- This paper size applies to Chinese national standards (CNS) A4 specification (210X 297 mm) 591338 A7 B7 V. Description of the invention (41) CF3S〇3 (difluoromethyl% acid radical = difluoromethane sulfonate xanthate) and πκ all gas butyl diacetate). Test / Interfacial Activity: The base and surfactant of the present invention can be used to improve imaging properties. Some available tests include tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, benzimidazole, 4-phenylpyridine, 4, diamine diphenyl ether, nicotinamide , 1-hexahydropyridylethanol, triethanolamine, hexahydropyridinyl 2-propanediol, 2,2,6,6-tetramethylhexahydropyridinol, tetrabutylammonium hydroxide, tetrabutylammonium acetate and Tetrabutylammonium lactate. Some useful surfactants include ammonium perfluorooctanoate, ammonium perfluorononanoate, ZONYL (g) (trade name of DuPont) FSA, FSN, FSO, and FSK fluorine-based surfactants, polyethylene oxide stearin Base acid, polyethylene oxide oleyl ether, polyethylene oxide octyl phenyl mystery, polyethylene oxide nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol monostearate, tiger benzene Dibasic acid salts, dibasic sodium succinate and sodium lauryl sulfate. The test surfactant may be present in an amount of about 0.001 to about 5.0%, typically about 0.001 to about 2.0%, based on the weight of the entire composition. Dissolution Inhibition 1 Various dissolution inhibitors can be used in the present invention. Ideally, dissolution inhibitors (PI) for far and extreme UV photoresists (such as 193nm photoresist) are designed / selected to meet the multiple material needs of photoresist compositions including specific DI additives, including dissolution Inhibition, plasma etching resistance and adhesion behavior. Some dissolution inhibiting compounds also act as plasticizers in photoresist compositions. -45- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 591338 A7 B7 V. Description of the invention (42)

A variety of bile salt esters (i.e., bile esters) are particularly useful as DI in the compositions of the present invention. Bile salts and esters are known to be effective dissolution inhibitors for far-UV photoresistance, starting with the research work of Reichmanis et al. "The role of photosensitivity in resistance", J. Electrochem. Soc. 1983, 130, 1433-1437). Bile salt esters are particularly attractive choices for DI systems, for several reasons, including their availability from natural sources, their high cycloaliphatic carbon content, and their particularly high range in the electromagnetic spectrum and in the vacuum UV region. Transparent (for example, it is typically highly transparent at 193 nm). Furthermore, bile salt esters are also attractive DI choices, as they can be designed to have a wide range of hydrophobic to hydrophilic compatibility, depending on hydroxyl substitution and functionalization. Order

Threads are suitable as representative bile acids and bile acid derivatives of the additives and / or dissolution inhibitors of the present invention, including but not limited to those shown below, which are as follows: · Cholic acid (IV), deoxycholic acid (V), Lithocholic acid (VI), tertiary-butyl deoxycholate (VII), tertiary-butyl lithocholic acid (VIII), and tertiary-butyl 3-α-ethylithocholate (IX). Bile acid esters, including compounds VII-IX, are preferred dissolution inhibitors in the present invention.

Derolled cholic acid -46- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 591338

The amount of inhibitor t can be changed according to the choice of polymer. When the polymer lacks α Λ generation and field formation, the image formation properties of the dissolution inhibitor 乂 Likou strong photoresist composition. 2. The composition of the invention of Y may contain other optional ingredients. Examples of other ingredients that can be added include, but are not limited to, resolution enhancers, adhesion promoters, residue reducing agents, coating aids, plasticizers, and Tg (glass transition temperature) modifiers. A cross-linking agent may also be present in the negative-acting photoresist composition. Some typical cross-linking agents include bisazides, such as 4,4f-diazidediphenyl sulfide and 3,3-azidediphenylimide. Typically, negative handling compositions containing at least one cross-linking agent also contain suitable functional groups (such as unsaturated C = C bonds) that can react with reactive species (such as nitrogenenes) that are generated when exposed to UV. React to produce a crosslinked polymer that is insoluble, dispersible, or substantially swellable in the developer solution. The method of making a photoresist after the photoresist is formed on the substrate, including the following sequence: -47- This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm)

Description of the Invention (X) The photoresist layer is exposed by image replication to form imaged and unimaged areas, wherein the photoresist layer is made from a photoresist composition comprising: (A) selected from the group consisting of (E) polymers and mixtures thereof; (B) photoactive ingredients; (C) functional compounds selected from the group consisting of alkalis and surfactants; and 00 to provide exposed photoresist with imaged and unimaged areas Layer display

Image 'to form a relief image on the substrate. Therefore, the photoresist layer is made by applying a photoresist composition to a substrate and drying to remove the agent. The photoresist layer thus formed is sensitive in the ultraviolet region of the electromagnetic spectrum, and especially for wavelengths of $ 365 nanometers. The image reproduction exposure of the photoresist composition of the present invention can be achieved at many different UV wavelengths, including but not limited to 365 nm, 248 nm, 193 nm, 157 nm and lower wavelengths. Exposure by image reproduction, preferably achieved with UV light of 248 nm, 193 nm, 157 nm or lower wavelength, and more preferably achieved with UV light of 193 nm, 157 nm or lower wavelength , And the best is achieved with 157 nm or lower wavelength ultraviolet light. Image copying Exposure can be achieved either numerically using a laser or equivalent device, or non-numerically using a photomask. Numerical imaging using lasers is preferred. Suitable laser devices for numerical imaging of the composition of the present invention include, but are not limited to, argon-fluorine lasers using UV output at 193 nm, and thorium-fluorine lasers using UV output at 248 nm , And fluorine (F2) laser, use output at 157 nm. As discussed above, due to the use of lower wavelengths -48- this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 591338 A7

UV light for image reproduction exposure is equivalent to higher resolution (at resolution =), so using lower wavelengths (eg 193nm or 157nm or lower) is better than using higher wavelengths (eg 248 nm or higher). The ingredients in the photoresist composition of the present invention must contain sufficient functionality, 'to be developed after the image is copied and exposed to UV light. This functional group is an acid or a protected acid compared to 2, so that aqueous imaging can use alkaline imaging, such as sodium hydroxide solution, potassium hydroxide solution, or ammonium hydroxide solution. For example, the polymer (c) in the photoresist composition of the present invention is typically an acid-containing shellfish containing at least one fluorine-containing alcohol monomer, and has the following structural units:

-C (Rf) (Rf,) OH The center and Rf are as described above. The content of acidic fluoroalcohol groups is measured for a specific composition by optimizing the amount required for good development in an aqueous alkaline developer. When a water-processable photoresist is coated or otherwise applied to a substrate and exposed to UV light by image reproduction, the development of the photoresist composition may require that the adhesive substance should contain sufficient Acid groups (such as fluoroalcohol groups) and / or protected acid groups, which are at least partially removed from protection during exposure, so that the photoresist (or other photoimageable coating composition) can Processing in sexual imaging agents. In the case where the photoresist layer is positively operated, the photoresist layer is removed during the development, and the portion exposed to the UV radiation is removed, but the unexposed portion is not substantially changed during the development. -49-This paper size is in accordance with China National Standard (CNS) A4 (2l0x297 mm) 591338 A7 B7 V. Description of the invention (46) Affected by the direction of the image, this image is obtained by using an aqueous alkaline liquid, such as containing 0.262 N aqueous solution of tetramethylammonium hydroxide (where the imaging system is at 25 ° C and usually takes less than or equal to 120 seconds). In the case of a negative-acting photoresist layer, the photoresist layer is removed during the development and is not exposed to UV radiation, but during the development, the exposed portion is essentially It is unaffected by the development, and the development system uses a critical fluid or an organic solvent. A critical fluid, as used herein, is one or more substances that are heated to a temperature near or above their critical temperature and compressed to a pressure near or above their critical pressure. The critical fluid in the present invention is a temperature higher than 15 ° C at least below the critical temperature of the fluid, and a pressure higher than 5 atm below the critical pressure of the fluid. Carbon dioxide can be used as a critical fluid in the present invention. Various organic solvents can also be used as the developer in the present invention. These include, but are not limited to, dentinizing solvents and dissolving solvents. Toothed solvents are typical, while fluorinated solvents are more typical. Substrate The substrate used in the present invention is, for illustrative purposes, silicon, silicon oxide, silicon nitride, or various other materials used in semiconductor manufacturing. Example Lexical Analysis / Measurement bs δ 8

NMR iHNMR 13 C NMR -50- This paper size is applicable to China National Standard (CNS) A4 (210X297 mm)

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line

Broad singlet NMR chemical shift measured in indicated solvent g Nuclear magnetic resonance proton NMR Carbon-13 NMR 591338 A7 B7 V. Description of the invention (47) 19fnmr S sec. M mL mm Fluorine-19 NMR multiple peak millimeter millimeter T 丄 g Mn Mw P = Mw / Mn absorption system ▲ glass transition temperature number of specific polymers average molecular weight specific polymers weight average molecular weight polydispersity of specific polymers AC = A / b where A is absorbance = Log10 (l / T), and b = film thickness (micrometers), where T = light transmittance, as defined below. Transmittance Transmittance T = the ratio of the radiant power transmitted by the sample to the radiant power incident on the sample, and it is a measure of a specific wavelength (eg nanometer). Chemicals / Monomer AA Acrylic acid AIBN Aldrich Chemical Company (Milwaukee, WI) 2,2'-Azobisisobutyronitrile Aldrich Chemical Company (Milwaukee, WI) CFC-113 1,1,2-trifluorotrifluoroethane HFIBO MEK (EI du Pont de Nemours (Wilmington, DE) hexafluoroepoxyisobutane 2-butanone NB Aldrich Chemical Company (Milwaukee, WI) n-pinene = bicyclo [2.2.1] hept-2-ene Aldrich Chemical Company (Milwaukee, WI) Perkadox® 16 N Di- (4-tertiary-butylcyclohexyl) peroxydicarbonate Noury Chemical Company (Burt, NY) PGMEA Propylene Glycol Methyl Ether Acetate One: tBA TCB Aldrich Chemical Company (Milwaukee, WI) Tertiary-Butyl Acrylate Trichlorobenzene-51-This paper size applies Chinese National Standard (CNS) A4 (210 x 297 mm) 591338 A7 B7 V. Description of the invention (48 TFE Aldrich Chemical Company) (Milwaukee, WI) Tetrafluoroethylene THF (E. I. du Pont de Nemours, Inc. (Wilmington, DE) Tetrahydro Vran® 52 Aldrich Chemical Company (Milwaukee, WI) 2,4-dimethyl-2,2 '-Azobis (valeronitrile) (E. I. du Pont de Nemours (Wilmington, DE) f3 NB-F-0-t-BuAc ^ s.0CH2C0CH2C02C (CH3) 3 QT ^ ip3 NB-F-O-t-BuAc ^ Yy ^ CH20CH2C0CH2C02C (CH3) 3

Kp cf3

CH2X

NB-Me-OH, X = 〇H

NB-Me-F-OH X = 〇CH2C (CF3) 2〇H NB-Me-F-OMOM X = 〇CH2C (CF3) 2OCH2OCH3

NB ^ OAc X = OCOCH3

NB-OH X = 〇H

NB-F-OH X: OCH2C (CF3) 2〇H NB-F-OMOM. X = 〇CH2C (CF3) 2OCH2〇CH3

VB-F-OH CH2CHOCH2CH2OCH2C (CF3) 2〇H VE-F-OMOM CH2 = CHOCH2CH2OCH2C (CF3) 2〇CH2OCH3 Ultraviolet light Extreme UV The region of the ultraviolet electromagnetic spectrum in the range from 10 nm to 200 nm The region of the UV electromagnetic spectrum in the ultraviolet light, which ranges from 200 nm to 300 nm. The region of the UV electromagnetic spectrum, which ranges from 10 nm to 390 nm. The region of the near UV electromagnetic spectrum in the ultraviolet light. The range is from 300nm to 390nm -52- This paper size applies to China National Standard (CNS) A4 (210x 297 mm) 591338 A7 B7 V. Description of the invention (49) Example 1: TFE / NB-F Synthesis of -OH / tBA trimer The synthesis of NB-F-OH is as follows: A dry round bottom flask equipped with a mechanical stirrer, an addition funnel and a nitrogen inlet tube is vented with nitrogen and charged to 197 grams ( (078 mole) 95% sodium hydride with 500 ml of anhydrous DMF. The stirred mixture was allowed to cool to 5t :, and 80.1 g (0.728 mol) of exo-5-n-assono-2-ol was added dropwise so that the temperature was kept below 15C. The resulting mixture was dropped for / 2 hours, and HFIB0 (131 g, 0.728 mol) was added dropwise at room temperature. The resulting mixture was stirred at room temperature overnight. Methanol (40 ml) was added and most of the DMF was removed on a rotary evaporator under reduced pressure. The residue was treated with 200 ml of water and glacial acetic acid was added until the pH was about 8.0. The aqueous mixture was extracted with 3 X 150 ml of ether. The combined ether extracts were washed with 3 X 150 ml of water and 150 liters of brine, dried over anhydrous sodium sulfate, and concentrated on a rotary evaporator to an oil. Diatomite distillation was performed at 0.15-0.20 Torr and a pot temperature of 30-60 ° C to obtain 190.1 g (90%) of the product. 1HNMR (5CD2C12) 1.10-1.30 (m, 1H), 1.50 (d, 1H), 1.55- 1.65 (m, 1H), 1.70 (s, 1H), 1.75 (d, 1H), 2.70 (s, 1H ), 2.85 (s, 1H), 3.90 (d, 1 H), 5.95 (s, 1H), 6.25 (s, 1H). Another sample prepared in the same manner was subjected to elemental analysis. Calculated values: C, 45.53; H, 4.17; F, 39.28. Found: C, 44.98; H, 4.22; F, 38.25. The synthesis of NB-F-OH is described in PCT Int. Appl. WO 2000067072 (published November 9, 2000). Add 48 · 7 g of the above to a 200 ml stainless steel autoclave -53- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm)

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Line 591338 A7 B7 V. Description of the invention (50) (0.168 mole) NB-F-OH, 1.54 g (0.012 mole) tertiary-butyl acrylate (tBa, Aldrich Chemical Company), 75 ml 1, 1,2-trichlorotrifluoroethane, and 0.6 g of Perkadox®16. The container was sealed, cooled, evacuated and purged with nitrogen several times. Then, 42 g (0.42 mol) of tetrafluoroethylene (TFE) was added. Stir the autoclave with the contents of the container at 50 ° C for about 18 hours, causing the pressure to change from 294 psi to 271 psi. Allow the container to cool to room temperature and vent to atmospheric pressure. Rinse with 1,1,2-trichlorotrifluoroethane to remove the contents of the container to obtain a clear solution. This solution was slowly added to excess hexane, causing white polymers to precipitate and allowed to dry in a vacuum oven overnight. The output is 11.3 grams (12%). GPC analysis: Mn = 7300; Mw = 10300; Mw / Mn = 1.41. DSC analysis: On second heating, Tg was found to be 135 ° C. Fluorine NMR spectrum showed absorption peaks at -75.6 ppm (CF3) and -95 to -125 ppm (CF2), confirming the incorporation of NB-F-OH and TFE. This polymer was analyzed by carbon NMR, and by integration of appropriate absorption peaks, it was found to contain 39 mole% TFE, 42 mole% NB-F-OH, and 18 mole% tBA. Analytical measured values: C, 43.75; H, 3.92; F, 40.45. Example 2: Terpolymer of TFE, NB-F-OH and tertiary-butyl acrylate, made using the following procedure: About 270 ml In the metal pressure vessel of Rongzhang, 71.05 g of NB-F-OH, 0.64 g of third-butyl acrylate, and 25 ml of 1,1,2-trichlorotrifluoroethane were added. The container was sealed, cooled to about -15 ° C, pressurized to 400 psi with nitrogen, and evacuated several times. The reactor was heated to 50 ° C and TFE was added until the internal pressure reached 340 psi. Dilute the used 1,1,2-trichlorotrifluoroethane -54- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Pretend

Line 591338 A7 B7 V. Description of the invention (51) to 100 ml of a solution of 75.5 g of NB-F-OH and 9.39 g of tertiary butyl acrylate, pumped to the reactor at a rate of 0.10 ml / minute, after 12 hours. At the same time as the start of the monomer feed solution, at the same time, a solution of 6.3 g of Perkadox® 16N and 30-35 ml of methyl acetate which has been diluted to 75 ml with 1,1,2-trifluorotrichloroethane, at 2.0 ml / Pumped to the reactor at a rate of minutes for 6 minutes and then at a rate of 0.08 ml / minute for 8 hours. By adding TFE, keep the internal pressure at 340 psi as needed. After a reaction time of 16 hours, the container was cooled to room temperature and evacuated to 1 atmosphere. The recovered polymer solution was slowly added to an excess of hexane while stirring. The precipitate was filtered, washed with hexane, and dried in a vacuum oven. The resulting solid was dissolved in a mixture of THF and 1,1,2, trichlorotrifluoroethane and slowly added to an excess of hexane. The precipitate was filtered, washed with hexane, and dried in a vacuum oven overnight to obtain 47.5 g of a white polymer. From its 13C NMR spectrum, it was found that the polymer composition was 35% TFE, 42% NB-F-OH, and 22% tBA. DSC: Tg = 151 ° C. GPC: Μη = 6200; Mw = 9300; Mw / Mn = 1.50. Analytical measured values: C, 44.71; H, 4.01; F, 39.38. Example 3: A homopolymer of NB-Me-Ff-OH was prepared using the following procedure: Under nitrogen, 0.19 g (0.49 mmol) Ear) allylpalladium complex [7? 3-MeCHCHCH2) PdCl] 2 and 0.34 g (0.98 mmol) of silver hexafluoroantimonate were suspended in chlorobenzene (40 ml). The resulting mixture was stirred for 30 minutes at room temperature. It was then filtered to remove the precipitated AgCl and an additional 10 mL of gaseous benzene was added. Add the resulting solution to 15.0 grams (49.0 millimoles) of NB-Me- -55- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

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Line 591338 A7 B7 V. Description of the invention (52)

F-OH. The resulting reaction mixture was stirred at room temperature for three days. The crude polymer was isolated by precipitation in hexane. This material was dissolved in acetone to obtain a 10% by weight solution and filtered through a 0.2 micron Teflon® filter; then, the acetone filtrate was concentrated to dryness to obtain 7.8 g of an addition copolymer. GPC: Mn = 6387; Mw = 9104; Mw / Mn = 1.43. Analytical and measured values: C, 46.28; H, 4.81; F, 34.22. The 1 H NMR (CD2 Cl2) of the polymer is consistent with the saturated vinyl addition polymer shown below:

Binding

The linear NB-F-OH / NB-F-0-t-BuAc copolymer was modified by the polymer and synthesized using the following procedure: On a 500 ml round bottom with a mechanical stirrer, liquid addition funnel and reflux condenser In the flask, 53.6 grams of NB-F-OH ethyl ethynyl addition homopolymer was calculated to contain 0.185 moles of hexafluoroisopropanol, 200 ml of acetonitrile, and 30.6 grams (0.222 moles) of potassium carbonate. This mixture was refluxed for 0.5 hours. Tertiary-butyl bromoacetate (10.8 g, 0.055 mole) was added dropwise, and the resulting mixture was refluxed for 3 hours. The mixture was allowed to cool to room temperature and diluted by adding-300 ml of acetone. The mixture was then filtered and concentrated under vacuum to a volume of about 200 ml. Slowly pour this concentrated mixture into 5.4 liters -56- This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) 591338 A7 B7 V. Description of the invention (53) 1.0% HC1 aqueous solution. The formed precipitate was filtered and washed with water. Then, the precipitate was dissolved in 200 ml of acetone; to this solution was added a solution of 5 ml of water and 3 ml of a 36% HC1 aqueous solution. The resulting solution was slightly cloudy. Pour it into 5.4 liters of water. The precipitate was washed several times with water and dried to obtain 44.0 g of an NB-F-OH / NB-F-0-t-BuAc copolymer. 1 9F NMR (5 Acetone-d6)-/373.1 (s, designated as a unit derived from NB-F-0-t-BuAc), -75.4 (s, designated as a unit derived from NB-F-OH). Through the integration of the spectra, the polymer composition was found to be 64% NB-F-OH and 36% NB-F-0-t-BuAc. The polymer sample was spin-coated from a 5% solution of 2-heptanone. The absorption coefficient at 157 nm is 3.15 μm at a film thickness of 47.2 nm, and at a film thickness of 45.7 nm is 2.70 μm4. Example 5: NB-Me-F-OH / NB-Me-F-0-t-BuAc copolymer was synthesized by polymer modification using the following procedure: Example 4 was repeated with the following exceptions: use NB-Me-F-OH vinyl addition homopolymer instead of NB-F-OH vinyl addition homopolymer to synthesize NB-Me-F-OH / NB-Me-F-0-t-BuAc Copolymer. 1 9 F NMR ((5 acetone-d6) -73.2 (s, specified as a unit obtained from NB-Me-FOt-BuAc), -75.3 (s, specified as a unit obtained from NB-Me-F-OH) By spectral integration, the polymer composition was found to be 68% NB-Me-F-OH and 32% NB-Me-F-0-t-BuAc. Example 6: The following solutions were prepared and magnetically stirred overnight. Ingredient weight (G) -57- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

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Line 591338 A7 B7 V. Description of the invention (%) TFE / NB-F-OH / tBA copolymer (weight ratio: feed 70/28/2; analysis by 13 C NMR, 39/42/18), as in Example 1 The 0.520 2-heptanone solution of perfluorooctanoic acid ammonium salt (0.011% by weight) as described in 5.121 Tertiary-butyl lithocholic acid 0.060 Triphenylsulfonyl nonafluoroalkanesulfonate dissolved in cyclohexanone 6.82% (wt. ) Solution, which has been filtered through a 0.45 micron PTFE syringe filter for 0.299 spin coating using a Brewer Science 100CB combination spin coater / heating plate on a 4-inch diameter "P" type &lt; 100 &gt; oriented silicon wafer Yes, development was performed on a photoresist development analyzer (type 790) from Litho Tech. This wafer was fabricated in the following manner, depositing 6 ml of hexamethyldisilazane (HMDS) primer, and rotating at 5000 rpm for 10 seconds. Then, after filtering through a 0.45 micron PTFE syringe filter, about 3 ml of the above solution was deposited, rotated at 3000 rpm for 60 seconds, and baked at 120 ° C for 60 seconds. 248 nm imaging is achieved by exposing the coated wafer to light, which is obtained by exposing broadband UV light from an ORIEL 82421 solar simulator (1000 watts) through a 248 nm interference filter Obtained, the filter passes about 30% of the energy at 248 nm. The exposure time was 30 seconds, providing an unattenuated dose of 20.5 mJ / cm². The use of 18-position covers with different neutral optical densities produces a wide variety of exposure doses. After the exposure, the exposed wafer was baked at 120 ° C for 120 seconds. The wafer was developed in a tetramethylammonium hydroxide (TMAH) aqueous solution (ONKA NMD-3, 2.38-% TMAH solution) and developed for 60 seconds to produce a positive image. Example 7: -58-This paper size applies to China National Standard (CNS) A4 (210X 297 mm)

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Line 591338 A7 B7 V. Description of the invention (55) The following solutions were prepared and magnetically stirred: Ingredient weight Γ g) TFE / NB-F-OH / tBA copolymer (35/42/22, when analyzed by 13 C NMR 5.) A solution of 5.562 2-heptanone 48.652 triphenylsulfonium nonafluorosulfonate dissolved in 2-heptanone was prepared in a manner similar to that described in Example 2. It had passed 0.45 A microliter PTFE syringe filter was used to filter 2.842. To 5.0 samples of ten of the above solutions, 0.107 g of a 0.0232M solution of one of the following bases, which had been dissolved in 2-heptanone, was added. WI), and stirred overnight: A. trioctylamine F. 2,2,6,6-tetramethylhexahydropyridine B. triethanolamine G. 2,2,6,6-tetramethylpyridinol C. 1-hexahydropyridine ethanolΗ. 1-propyl-4-hexahydropyridone D. 3-hexahydropyridyl-1,2-propanediol I. tetrabutylammonium lactate * E. 1-hexahydropyridine Propionitrile J. Tetrabutylammonium hydroxide * is prepared by adding tetrabutylammonium hydroxide to ethyl lactate, and the formed sample is spin-coated on a substrate. Spin coating was performed on a 4-inch diameter "P" type &lt; 100 &gt; oriented silicon wafer using a Brewer Science 100CB combined spin coater / orifice hot plate. The imaging was performed by Litho Tech Japan Photoresist development analyzer (type 790).

The wafer was made in the following manner, depositing 6 ml of hexamethyldisilazane (HMDS) primer, and rotating at 1000 rpm for 5 seconds, and then at 3500 rpm for 10 seconds. Next, 1-3 ml of the above solution was passed through 0.2 micron PTFE -59- this paper size using Chinese National Standard (CNS) A4 (210 X 297 mm)

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Line 591338 A7 _B7_ V. Description of the invention (56) After being filtered by the syringe filter, it is deposited, rotated at 1800 rpm for 60 seconds, and baked at 120 ° C for 60 seconds. 248 nm imaging is achieved by exposing the coated wafer to light, which is achieved by passing broadband UV light from the ORIEL 82421 solar simulator (1000 watts) through a 248 nm interference filter And obtained, the filter passes about 30% of the energy at 248 nm. The exposure time was 10 seconds, providing an unabated dose of 13.5 millijoules / cm2. The use of 18-position covers with different neutral optical densities produces a wide variety of exposure doses. After the exposure, the exposed wafer was baked at 100 ° C for 60 seconds. The wafers were developed in a tetramethylammonium hydroxide (TMAH) aqueous solution (Shipley, LDD-26W developer, 0.26N TMAH solution) for 10 seconds. This test produces a positive image, in which the following light transmission doses (mJ / cm²) are required for the formulation with the above test: A · 3.9 mJ / cm² F · 3.9 mJ / cm² B. 3.2, , G. 3.9 ”C. 2.4”, H. 2.4 ”D. 3.2” I. 5.3 ”E · 6.8” J. 2.4 丨 Formulas' which contain a trimer similar to that described in this example and the above test It was exposed, developed and tested in a manner similar to that described in Example 9, and showed improvements in analysis. Example 8: Example 7 was repeated with the following exceptions: The following solutions were prepared and magnetically stirred: -60 -This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 591338 A7

Weight (g) 6.607 46.983 3.410 Composition NB-Me-F-OH / NB-Me-FO-Ac-tBu copolymer (68/32, when analyzed by 1 9 ρ NMR) is similar to that described in Example 5 2- Heptenone has a 6.82% (by weight) solution of triphenylsulfadecanesulfonate in 2-heptanone, which has been filtered through a 0.45 micron PTFE syringe filter in 5.0 grams of ten of the above solutions Add 〇128 克 〇232M dissolved

The liquid was disclosed in Example 7 and was dissolved in one of the bases in xanthone and stirred overnight. The wafer was coated and prepared as described in Example 7, except that the exposure time was 3 seconds' instead of 10 seconds, providing an unattenuated dose of 40 mJ / cm2. This test produces a positive image, in which the following light transmission doses (mJ / cm²) are required for the formulation with the above base: A · 2.4 mJ / cm² F. 2.1 mJ / cm² B. 1.2 ”G 1.2 ”C. 1.0” H. 1.2 MD · 1.2 ”I. 2.4” E. 2.1, J · 2.4, · Case A ·

The following solutions were prepared by wire, and magnetically stirred overnight, and filtered through a 0.45 micron PTFE syringe filter before use: Ingredient weight (g) NB-Me-F-OH / NB-Me-F-0-tBuAc (68/32 ) Copolymer, similar to Example 5, made 1.739 2-heptanone 12.364 -61-This paper size applies to China National Standard (CNS) A4 (2i0x 297 public love) 591338 A7 B7 V. Description of the invention (58) A 6.82% (by weight) solution of triphenylphosphonium nonafluorosulfonate in cyclohexanone, which has been filtered through a 0.45 micron PTFE syringe filter to 0.897

This photoresist formulation was spin-cast on an 8-inch Si wafer at 2000 rpm, and after PAB at 120 ° C for 60 seconds, a film with a measured thickness of 2169 A was produced. All imaging and open-frame exposures were performed using an Exitech 157 nm microstepper. A photoresist formulation was spin-coated on an 8-inch Si wafer, which was first vapor-primed at 90 ° C using hexamethyldisilazane (HMDS). The formed film is lightly baked or post-coated (PAB) for 60 seconds at 120 ° C, and then the thickness is measured using a Prometrix interferometer, which is measured using a variable angle spectrum ellipse measurement Method, using the JA Woollam VU301 variable-angle spectroscopic ellipsometry, the Cauchy coefficient measured. On an Exitech stepper, open frame exposure (typically 100 exposure doses), or use a binary cover with either numerical aperture (NA) = 0.6 and partial coherence (σ) = 0.7, or have After imaging the Levenson strong phase shift cover with NA = 0.6 and σ = 0.3, the wafer was subjected to post-exposure baking (PEB) at 100 ° C for 60 seconds, followed by Shipley LDD-26W 2.38% tetramethyl hydroxide 60 seconds of ammonium puddle imaging. Then, the exposed wafer is subjected to thickness measurement on a Prometrix interferometer to determine the thickness loss versus the exposure dose, and the imaged wafer is inspected using a JEOL 7550 top-down and tilt scanning electron microscope (SEM). And in some cases, cross sections were made and inspected using Hitachi 4500 SEM. At an exposure dose of 24 millijoules per square centimeter, it was found that the image showed a characteristic at 140 nm resolution. -62- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

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Example 9B uses the same polymer formulation, but adds 38 microliters of 0.5% by weight tetrabutylammonium lactate (TBALac) base to 1 ml of this photoresist. This corresponds to a molar concentration of alkali equal to 10% of the molar concentration of PAG. This formulation was spin-cast on an 8-inch Si wafer at 2000 rpm. After 60 seconds of PB at 120 ° C, a film thickness of 2087 A was produced. The film was exposed and developed as described above. Then, the formed image was examined in a JEOL 7550 SEM, and it was found that at an exposure dose of 52 mJ / cm2, it showed characteristics as low as 60 nm. These features are also examined with a Hitachi 4500 SEM in cross section. The 100 nm 1: 2 lines and gaps are well resolved and show good line distribution, as in the case of 60 nm 1: 5 lines and gaps. These results confirm that this vinyl addition polymer, when formulated with the added base, can be imaged at sub-100 nm resolution and has a film thickness of more than 200 nm.

Example 9C Using one and a half of the added TBALac base, another experiment was performed, and the imaging quality was shown to be in the middle of the results without the added base and 10 mole% PAG added base. Can analyze 100 nanometers 1: 5 lines and gaps.

Example 9D Another experiment was performed in which the same initial polymer formulation (resin and PAG in 2-heptanone) was used, but 10 mole% PAG plus tetrabutylammonium hydroxide (TBAOH) was used instead of TBAlac. The resulting image shows a resolution of 100 nm 1: 3 lines and gaps.

Example 9E Open Frame Exposure (Dose vs. Transparency Ep and Photoresistance Comparison): -63- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

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Line 591338 A7 B7 V. Description of the invention (60) Once again, the above formulation is prepared on a slightly larger scale. This photoresist compound was spin-cast on an 8-inch Si wafer at 2000 rpm, and after PAB at 120 ° C for 60 seconds, a film with a measured thickness of 2169 A was produced. Then, in an Exitech stepper, the film was exposed to 157 nm radiation in 10x10 open-frame format, using an exposure dose change from 0 to 10 mJ / cm2, in 0.1 mJ / cm2 increments. After exposure, the film was subjected to PEB at 100 ° C for 60 seconds, and then developed in a Shipley LDD-26W for puddle development for 60 seconds. Using a Prometrix interferometer, the resulting image was examined to measure the thickness of the film remaining after development at all 100 exposure dose locations. The data formed showed that at an exposure dose of 7.4 mJ / cm2, the film system with 0% plus alkali was completely removed by the developer (E0 = 7.4 mJ / cm2).

Example 9F A second formulation was prepared by using 4 ml of the same solution described above and adding it to 154 microliters of a 0.5 wt% solution of TBALac in 2-heptanone. This results in a photoresist formulation having a base concentration equal to 10 mole% of the PAG concentration. This photoresist formula was spin-washed on an 8-inch Si wafer at 2000 rpm. After PAB at 120 ° C for 60 seconds, a film with a measured thickness of 2003 A was produced. Then, in an Exitech stepper, the film was exposed to 157 nm radiation in a 10x10 open-frame format using an exposure dose change from 0 to 30 mJ / cm2 in 0.3 mJ / cm2 increments. After the exposure, the film was subjected to PEB at 100 ° C for 60 seconds, followed by water-hole development in Shipley LDD-26W for 60 seconds. Examine the formed image with a Prometrix interferometer to measure all 100 exposure doses after development. -64- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

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Line 591338 A7 B7 V. Description of the invention (61) The thickness of the film left behind. The resulting data show that at a exposure dose of 25.8 mJ / cm², a film with 10% plus alkali was completely removed by the developer (E0 = 25.8 mJ / cm²).

Example 9G A third formulation was prepared by using 3 ml of the same solution described above and adding it to 90 microliters of a 0.5% by weight TBAOH solution in 2-heptanone. This results in a photoresist formulation having a base concentration equal to 10 mole% of the PAG concentration. This photoresist formulation was spin-cast on an 8-inch Si wafer at 2000 rpm, and after 60 seconds of PAB at 120 ° C, a film with a measured thickness of 2001 A was produced. Then, in an Exitech stepper, the film was exposed to 157 nm radiation in 10x10 open-frame format, using an exposure dose change from 0 to 30 mJ / cm², in increments of 0.3 mJ / cm². After the exposure, the film was subjected to PEB at 100 ° C for 60 seconds, followed by puddle development in Shipley LDD-26W for 60 seconds. Using a Prometrix interferometer, the resulting image was examined to measure the thickness of the film remaining at all 100 exposure dose positions after development. The data formed shows that at a dose of 18.3 mJ / cm², a film with 10% plus alkali was completely removed by the developer (EQ = 18.3 mJ / cm²). In all cases, with the addition of alkali, the data confirm that the photoresist displays a high contrast when exposed to 157 nm light. High contrast is one of the desired characteristics in photoresist, which can cause high resolution imaging in semiconductor patterning, and these vinyl addition polymer photoresist formulations each have this desired property. -65- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

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Claims (1)

591338 A8 B8 C8 Patent application scope Nitrogen compounds, polymeric ammonia compounds, organic amines, organic ammonium hydroxides, salts with organic acids, and mixtures thereof. 4. The photoresist composition according to item 丨 of the patent application, wherein the surfactant has a positive, negative or neutral charge. 5. The photoresist composition according to item 4 of the patent application, wherein the surfactant is selected from fluorinated and non-fluorinated surfactants. 6. The photoresist composition as described in the first item of the scope of the patent application, wherein the polymer has an absorption coefficient of less than 50 microns at a wavelength of 157 nanometers. 7. The photoresist composition according to item 1 of the patent application scope, wherein the polymer ⑷ is a fluorinated copolymer that includes repeating units derived from at least one ethylenically unsaturated compound, and is characterized by at least one ethylenic unsaturated The compound is polycyclic, and at least one ethylenically unsaturated compound contains at least one fluorine atom, and is covalently connected to an ethylenically unsaturated carbon atom. 8. The photoresist composition according to item 1 of the patent application range, wherein the polymer 氟 is a fluorinated copolymer 'which contains repeating units derived from at least one polycyclic ethylfluorene unsaturated compound, the compound having at least one atom Or a group selected from the group consisting of a fluorine atom, a perfluoroalkyl group, and a perfluorofluorenyl group, characterized in that the at least one atom or group is covalently connected to a carbon atom ', this carbon atom system is included in the ring structure And are separated from each ethylenic unsaturated carbon atom of the ethylenic unsaturated compound by at least one carbon atom connected in a covalent manner. 9. The photoresist composition according to item 1 of the scope of the patent application, wherein the polymer ii) is a branched polymer containing a protected acid group, and the polymer includes — -67- 591338 ABCD VI. Patent Application Scope or multiple branched segments, chemically connected along the linear main segment. ο. The photoresist composition according to item 1 of the scope of patent application, wherein the polymer ⑷ is selected from the group consisting of: (cl) a fluorine-containing polymer comprising repeating units derived from at least one ethylenically unsaturated compound, the compound Contains a fluoroalcohol functional group and has the following structure: -C (Rf) (Rf00OH where Rf and Rf are the same or different fluorofluorenyl groups of 1 to 10 carbon atoms' or are used together as (CF2) n, Where η is 2 to 10; (c2)-a fluorinated copolymer 'comprising repeating units derived from at least one ethylenically unsaturated compound, characterized in that at least one ethylenically unsaturated compound is cyclic or polycyclic , At least one ethylenically unsaturated compound contains at least one fluorine atom, covalently connected to the ethylenically unsaturated carbon atom, and at least one ethylenically unsaturated compound contains a fluoroalcohol functional group, and has the following structure: -C ( Rf) (Rf ·) 〇H where 1 to 10 carbon atoms are the same or different fluorocarbon groups, or used together as (CF2) n, where η is 2 to 10; (c3)-a fluorine-containing copolymer, It contains: (i) Derived from at least one woman Repeating units of unsaturated compounds' This compound contains at least three fluorine atoms and is covalently connected to two ethylene-based unsaturated carbon atoms; ^ 重复 repeating units derived from ethylene-based unsaturated compounds, continued -68- this paper The scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 591338 8 8 8 8 AB c D 々, the scope of the patent application compound contains a fluoroalcohol functional group, and has the following structure: -C (Rf) (Rf, ) OH where Rf and Rf are the same or different fluoroalkyl groups of 1 to 10 carbon atoms, or are used together as (CF2) n, where η is 2 to 10; (c4) a fluorinated copolymer comprising a derivative From a repeating unit of at least one ethylenically unsaturated compound, the compound contains a fluoroalcohol functional group and has the following structure: -ZCH2C (Rf) (Rf,) OH where Rf and Rf are the same or 1 to 10 carbon atoms or Different fluoroalkyl groups, or (CF2) n, where η is 2 to 10; and Z is an element of Group VA or VIA of the periodic table; (c5) a fluorine-containing polymer, which contains the following structure: Each of R40, R41, R42, and R43 is independently a hydrogen atom, a halogen atom, a hydrocarbon group containing 1 to 10 carbon atoms, a substituted hydrocarbon group, an alkoxy group, a carboxylic acid, a carboxylic acid ester, or a function having the following structure Base: -C (Rf) (Rf,) OR44 where Rf and Rf are the same or different halothanes of 1 to 10 carbon atoms -69- This paper size applies Chinese National Standard (CNS) A4 specifications (210X 297 mm ) 591338 A8 B8 C8 D8 VI. Apply for a patent scope, or use together as (CF2) n, where η is 2 to 10; R44 is a hydrogen atom or an acid- or iso-stable protecting group; V is a repeating unit during polymerization Number in the body; w is 0-4; at least one repeating unit has a structure, wherein at least one of R40, R41, R42 and R43 contains a structure of C (Rf) (Rf.) OR44; and (c6)-a kind of polymer Which includes: (iii) a repeating unit derived from at least one ethylenically unsaturated compound containing a fluoroalcohol functional group and having the following structure: -C (Rf) (Rf,) OH where Rf and Rf are 1 To 10 carbon atoms of the same or different fluoroalkyl groups, or taken together as (CF2) n, where η is 2 to 10; and (iv) derived Repeating unit of at least one ethylenically unsaturated compound having the following structure: (H) (R45) C = C (R46) (CN) where R45 is a hydrogen atom or CN; R46 is a CrC8 alkyl group, a hydrogen atom, or a C02R47 group Where 1 ^ 7 is a Cl-C ^ group or an argon atom. 11. The photoresist composition according to item 10 of the patent application, wherein the polymer (c) further comprises a spacer selected from the group consisting of Otome, fumes, 1, Γ-disubstituted olefins, vinyl alcohols, vinyl groups Ethers and i, diene. 12. The photoresist composition according to item 1 of the scope of patent application, wherein the polymer (d) further comprises one or more comonomers CR51r5 2 = CR5 3 R5 4, wherein each of-R51, R52, R53 is independently selected from Η Or F, and where R54 is selected from the group consisting of -F, -CF3, -〇R) 5, where R5 5 is Cnp2n + 1, where n = 1 to -70- This paper size applies to China National Standard (CNS) A4 Specifications (210 x 297 public love) 591338 A BCD VI. Patent application scope 3, -0H (when R53 = H), and α (when R51, R52 and R53 = F). 13. The photoresist composition according to item 1 of the patent application scope, wherein the polymer (d) further comprises an amorphous vinyl copolymer selected from the group consisting of CH2 = CHCF3 and CF2 = CF2 in a ratio of 1: 2 to 2: 1 ; CH2 = CHF and CF2 = CFC1, with a ratio of 1: 2 to 2: 1; CH2 = CHF and CC1H = CF2, with a ratio of 1: 2 to 2: 1; perfluoro (2-methylenetolmethyl-1 , 3-dioxofluorene) in any ratio with perfluoro (2,2 · dimethyl-1,3-dioxofluorene); perfluoro (2-methylene-4-methyl-1, 3-dioxofluorene) is in any proportion with difluorovinylidene, which is amorphous; and a homopolymer of perfluoro (2-methyleneoxymethyl-1,3-dioxofluorene). 14. The photoresist composition according to item 1 of the scope of patent application, wherein the polymer (e) is selected from the group consisting of (el) a polymer comprising: (i) a repeat derived from at least one ethylenically unsaturated compound Unit, the compound contains a vinyl ether functional group and has the following structure: ch2 = cho-r56 where R56 is a substituted or unsubstituted alkyl, aryl, aralkyl, or alkaryl group, having 1 to 20 carbons Atom; and (ii) a repeating unit derived from at least one ethylenic unsaturated compound having the following structure: (h) (r57) oc (r58) (cn) where R5 7 is a hydrogen atom or a cyano group; R5 8 is A pit group 'C02 R? 9 group ranging from 1 to 8 carbon atoms, of which R5 9 is a carbon atom ranging from 1 to 8 -71-This paper size applies Chinese National Standard (CNS) A4 specifications (21G X 297 (Public Director) &quot; '591338 A8 B8 C8 __________D8_ Six patents for patent application ^ ~~-alkyl groups, or hydrogen atoms; and (iii) repeating units derived from at least one ethylenically unsaturated compound containing an acidic group; And (e2) — a kind of aggregates, comprising: (i) bamboo species from V to B species And the repeating unit of the compound, the compound contains a vinyl ether functional group and a fluoroalcohol functional group, and has the following structure: C (R6 0) (R6 1) = C (R6 2 &gt; 〇-DC (Rf) (Rf ,) OH where R60, R6i, and R62 are independently hydrogen atoms, alkyl groups ranging from 丨 to 3 carbon atoms; 〇 is at least one atom, which is connected to the vinyl ether functional group, passes the oxygen atom, and reaches the gas group The carbon atoms of the alcohol functional group, Rf and Rf, are the same or different fluorenyl groups containing 1 to 10 carbon atoms, or-as (α32) η, where n is an integer ranging from 2 to 10; and (H) A repeating unit derived from at least one ethylenically unsaturated compound having the following structure: (h) (r57) oc (r58) (cn) where R57 is a hydrogen atom or a cyano group; R58 is a range from 丨 to 8 A carbon atom alkyl group, a C02R59 group, where R59 is an alkyl group ranging from 1 to 8 carbon atoms, or a hydrogen atom; and (iii) derived from at least one ethylenically unsaturated compound containing an acidic group The repeating unit of the photoresist composition according to item 1 of the patent application range, wherein the photoactive component is chemically bound to the photoresist composition. Including the aggregates of (a) to (e); and -72- This paper size applies to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 591338 A8 B8 C8 _______D8 VI. Patent Application Scope-1 'Mixture . 16. · A method for preparing a photoresist image on a substrate, including the following sequence: (X) exposing the photoresist layer in an image copying manner to form imaged and unimaged areas, wherein the photoresist layer is made from A photoresist composition comprising: (A) a polymer selected from the group consisting of (a) a fluorinated copolymer comprising repeating units derived from at least one ethylenic unsaturated compound, characterized in that the at least one ethylenic The unsaturated compound is polycyclic; (b) a branched polymer containing a protected base, the polymer containing one or more branch bond segments, chemically connected along a linear main segment; (c) Fluoropolymer, which has at least one fluoroalcohol group, and has the following structure: -C (Rf) (Rf,) OH wherein Rf and Rf · are the same or different fluorocarbon groups of 1 to 10 carbon atoms, or are used together as (CF2) n, where η is 2 to 10; (d) perfluoro (2,2-monomethyl-1,% dilactate) or CX2 = CY amorphous vinyl homopolymer, where X = F or CF, and Y--H, or an amorphous vinyl group of perfluoro (2,2-dimethyl-i, 3-dioxolane) and CX2 = CY2 Polymers; and (e) / fluorinated alcohol-containing polymers' made from substituted or unsubstituted vinyl acids; and -73- This paper size applies to China National Standard (CMS) A4 (210 X 297 mm) (Centimeter) 591338 A8 B8 (B) a photoactive component; and (C) a functional compound selected from the group consisting of an alkali or a surfactant, and (Y) developing an exposed photoresist layer having imaged and unimaged areas to form a floating The convex image is on the substrate. 17. The method of claim 16 in the scope of patent application, wherein the test has a value of 5 or greater. 18. The method according to claim 17 in which the base is selected from the group consisting of monomeric nitrogen compounds, polymeric nitrogen compounds 'organic amines, organic ammonium hydroxide', salts thereof with organic acids, and mixtures thereof. 19. The method of claim 16 in which the surfactant has a positive, negative, or neutral charge. 20. The method of claim 19, wherein the surfactant is selected from fluorinated and non-fluorinated surfactants. 21. The method according to item 16 of the patent application, wherein the polymer has an absorption coefficient of less than 5.0 microns at a wavelength of 1 ”nanometer. 22. The photoresist composition according to the application patent, wherein the fluorinated copolymer (C4 Z) is sulfur, oxygen, nitrogen, or phosphorus. 23. For example, the photoresist composition of the scope of application for the patent, which further contains a solvent 0 -74- This paper size applies Chinese National Standards (CNs) A4 specifications (210X (297 mm) Binding Bulletin lh Application No. 75.IL ^ Case No. 090129535 Class 6i02 &gt; F Α4 C4 Amendment Supplementary Chinese Manual Replacement (February 1992) 591338 The above columns are filled by the Office) f1 Patent Specification-、 S name Chinese alkali and surfactant and photoresist composition for photolithography etc. English BASES AND SURFACTANTS AND THEIR USE IN PHOTORESIST COMPOSITIONS FOR MICROLITHOGRAPHY Name Nationality 1. Larry L. 2. Michael Carl Crawford MICHAEL KARL CRAWFORD 3. Frank L. Schrader, III FRANKL. SCHADT, III 4. Fletcher Klaus Susta, II FREDRICK CLAUS ZUMSTEG, JR. All American inventions &lt; name of creator, residence ( Name) Nationality 1 · No. 596, Meizhen Road, Chadsford, Pennsylvania, USA 2. No. 26 Jeremy Kecai Road, Granville, Pennsylvania, USA 3. Delaihuai Avenue, Weiming Town, Delaihuai, USA 2407 No. 4 · EI DU PONT DE NEMOURS AND COMPANY US DuPont Co., Ltd. 2715 Yinbian Road, Wilmington, Germany Come to Markard Street, Wilmington, Huaizhou 丨 〇 〇 7 Marian. Di. McNeihai MIRIAM D. MECONNAHEY Say A8 B8 C8 D8 1. A photoresist composition comprising: (A) a polymer selected from the group consisting of: (a) a fluorinated copolymer comprising repeating units derived from at least one ethylenically unsaturated compound , Characterized in that the at least one ethylenically unsaturated compound is polycyclic; ⑻ a branched polymer containing a protected acid group, the polymer containing one or more branched segments, chemically along a linear main Segment connection; (c) Fluoropolymer with at least one fluoroalcohol group, which has the following structure: where Rf and Rf are the same or different fluoroalkyl groups of 1 to 10 carbon atoms, or used together as (CF2) n, where 11 is 2 to 10; (d) Perfluoro (2,2-dimethyl-1,3-dioxolane) or Cx2 = Cy2 amorphous vinyl homopolymer, where X == F or CF3, and Y =, or an amorphous ethylene-based copolymer of perfluoro (2,2-dimethyl-1,3-dioxolene) and Cx2 = Cy2; and (e) nitrile / fluorine-containing A polymer of an alcohol based on a substituted or unsubstituted ethenyl ether; and (B) at least one photoactive ingredient; and (C) a functional compound selected from the group consisting of a base Surfactant. 2. The photoresist composition according to item 1 of the patent application scope, wherein the photoresist composition is at least 5. 3. The photoresist composition according to item 2 of the scope of patent application, in which the inspection system is selected from a single paper size applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm)